WO2020124468A1 - Crystal material, preparation method and use thereof, positive electrode material for sodium ion battery, sodium ion battery, and apparatus - Google Patents

Crystal material, preparation method and use thereof, positive electrode material for sodium ion battery, sodium ion battery, and apparatus Download PDF

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WO2020124468A1
WO2020124468A1 PCT/CN2018/122244 CN2018122244W WO2020124468A1 WO 2020124468 A1 WO2020124468 A1 WO 2020124468A1 CN 2018122244 W CN2018122244 W CN 2018122244W WO 2020124468 A1 WO2020124468 A1 WO 2020124468A1
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positive electrode
sodium
crystalline material
sodium ion
source
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PCT/CN2018/122244
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French (fr)
Chinese (zh)
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唐永炳
姚文娇
宋天一
吴南中
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深圳先进技术研究院
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of sodium ion batteries, in particular, to a crystalline material and its preparation method and use, positive electrode materials for sodium ion batteries, sodium ion batteries and equipment.
  • the secondary battery is also called a rechargeable battery, and is a battery that can be repeatedly charged and discharged and recycled.
  • Lithium-ion batteries are widely used in secondary batteries. They have the advantages of high energy density and long life. They have a wide range of applications in the field of energy storage, but the low natural abundance and uneven distribution of lithium make lithium-ion batteries cost. Increasing day by day. Sodium is located directly below lithium in the periodic table, and has similar chemical properties to lithium, and the crust is rich in reserves, and its abundance is about 1000 times that of lithium, so sodium ion batteries are expected to make up for the shortcomings of lithium ion batteries. A new generation of high-performance and low-cost energy storage technology.
  • the working principle of a sodium ion battery is similar to that of a lithium ion battery, and energy storage and release are realized through the redox reaction of sodium ions at the positive and negative electrodes.
  • the core components of sodium ion battery include positive electrode, negative electrode and electrolyte.
  • sodium ions are extracted from the positive electrode active material and embedded in the negative electrode active material; during discharge, sodium ions are extracted from the negative electrode active material and embedded in the positive electrode active material.
  • the design capacity of the negative electrode of the sodium ion battery should be higher than that of the positive electrode, so that the positive electrode material determines the capacity of the sodium ion battery.
  • the voltage of the sodium ion battery is the potential difference between the positive and negative electrode materials, and the higher the redox potential of the positive electrode material, the more favorable it is to obtain a high sodium ion battery voltage.
  • the structural stability of the cathode material is currently the main bottleneck in the development of sodium ion batteries.
  • the positive electrode material of sodium ion battery can be roughly divided into layered oxide, polyanion compound and organic positive electrode.
  • the types of anode materials for sodium ion batteries are limited, and the electrochemical performance is not ideal and the preparation process is relatively complicated.
  • the theoretical specific capacity of the layered oxide cathode material is relatively high, but high voltage can easily trigger irreversible oxygen release, which can cause battery failure.
  • Organic cathode materials have the problems of low operating voltage and poor thermal stability.
  • the polyanionic compound has a stable structure, and its polyanionic group can adjust the electrochemical reaction potential of the material through induction, and thus has excellent application prospects.
  • polyanion cathode materials for sodium ion batteries at this stage, and they are mainly concentrated in phosphate and sulfate systems. Their preparation process is complicated, the cost is high and the performance is not ideal.
  • the first object of the present application is to provide a crystalline material, which is a heterogeneous, hexagonal crystal system with a microscopic three-dimensional skeleton structure, in which sodium ions and water molecules do not participate in the formation of the skeleton, the crystal structure is rich in The holes are used for sodium ion migration.
  • the crystalline material can be used as a positive electrode active material of a sodium ion battery, which greatly improves the sodium insertion performance of the positive electrode active material containing the same, and improves the redox potential and structural stability of the positive electrode active material.
  • the second object of the present application is to provide a method for preparing a crystalline material.
  • the preparation method uses solvothermal synthesis of crystals, which has a simple process and low cost, and is suitable for industrial production.
  • the third object of the present application is to provide the application of the above-mentioned crystal material or the above-mentioned crystal material preparation method to the preparation of a positive electrode active material.
  • the fourth object of the present application is to provide a positive electrode material for a sodium ion battery, comprising the above crystalline material, or the crystalline material prepared by the method for preparing the crystalline material.
  • the fifth object of the present application is to provide a sodium ion battery including the above-mentioned sodium ion battery cathode material, which has the same advantages as the above-mentioned crystalline material or sodium ion cathode active material.
  • the sixth object of the present application is to provide a device including a sodium ion battery.
  • the present application provides a crystalline material with a chemical formula of Na 2 M(C 2 O 4 )X ⁇ nH 2 O, where M is at least one positive divalent metal and X is a negative divalent anion group Group, and X is not (C 2 O 4 ), 0 ⁇ n ⁇ 12;
  • the M is at least one positive divalent transition metal
  • the M is at least one of Ti, V, Cr, Mn, Co, Ni, Cu or Zn, or a combination of at least one of the foregoing metals and Fe;
  • X is (SO 4 ), (SeO 4 ), (PO 3 F), (HPO4), (HAsO 4 ), (MoO 4 ), (WO 4 ), (S 2 O 7 ) or ( Se 2 O 7 ) one of the anionic groups, 0 ⁇ n ⁇ 6;
  • the chemical formula of the crystalline material is Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, which belongs to the hexagonal crystal system, the space group is P-63m, and dehydration
  • the temperature is 180°C
  • the decomposition temperature is 300°C
  • the molar ratio of sodium source, M source, oxalate source and X source is (2-8):1:(1-8):(2-8);
  • the sodium source includes at least one of oxides, bases or salts containing sodium;
  • the M source includes at least one of M-containing oxides, acids, bases, salts, or M elements;
  • the oxalate source includes at least one of oxalate-containing acid or salt;
  • the solvent is at least one of water, alcohols, ketones or pyridines, preferably water.
  • the temperature of the solvothermal reaction is 100-300° C., and the time is 4-100 h.
  • the temperature of the solvothermal reaction is 180-220°C and the time is 48-72h.
  • the present application provides the above crystalline material, or the application of the crystalline material prepared by the above crystalline material preparation method in the preparation of a positive electrode active material.
  • the cathode active material, the cathode conductive agent and the cathode binder are included; the weight ratio of the cathode active material, the cathode conductive agent and the cathode binder is (60-90):( 5-30): (3-10); the positive electrode active material is the crystalline material;
  • the positive electrode conductive agent includes at least one of conductive carbon black, conductive carbon balls, conductive graphite, conductive carbon fiber, carbon nanotubes, graphene, or reduced graphene oxide;
  • the positive electrode binder includes at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber, or polyolefin .
  • the present application provides a device, including the above-mentioned sodium ion battery.
  • the chemical formula of the crystalline material provided in this application is Na 2 M(C 2 O 4 )X ⁇ nH 2 O (where M is at least one positive divalent metal ion, X is a negative divalent anion group, 0 ⁇ n ⁇ 12), the crystal material belongs to heterogeneous, hexagonal crystal system, with a microscopic three-dimensional skeleton structure, in which M, C 2 O 4 and X together constitute the skeleton, and sodium ions and water molecules do not participate in the formation of the skeleton.
  • the three-dimensional skeleton structure has abundant lattice channels for the migration of sodium ions, providing an effective path for the deintercalation and embedding of sodium ions.
  • the crystalline material can be used as a positive electrode active material of a sodium ion battery, which greatly improves the sodium insertion performance of the positive electrode active material containing the same, and improves the redox potential and structural stability of the positive electrode active material.
  • the positive electrode material for sodium ion battery provided by the present application includes the positive electrode active material prepared by the above crystalline material.
  • the positive electrode material for sodium ion battery has the advantages of high sodium insertion performance, high redox potential, good cycle stability and low cost.
  • the preparation method of the positive electrode active material provided by this application adopts the method of solvothermal synthesis of crystals.
  • the process is simple, the cost is low, and it is suitable for industrial production.
  • FIG. 1 is a schematic structural diagram of the crystalline material Na 2 M(C 2 O 4 )(SO 4 ) ⁇ nH 2 O provided by this application;
  • Example 2 is a crystal photograph of the crystalline material Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O provided in Example 1 of the present application;
  • Example 3 is a comparison diagram of the XRD spectrum and the theoretical spectrum of the crystalline material Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O provided in Example 1 of the present application;
  • thermogravimetric analysis diagram of the crystalline material Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O provided in Example 1 of the present application;
  • FIG. 5 is a cycle stability test chart of the sodium ion half-cell of Example 21 of the present application.
  • the percentage (%) or part refers to the mass percentage or part by weight relative to the composition.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “6-22” means that all real numbers between “6-22” have been listed in this article, and “6-22" is just an abbreviated representation of these numerical combinations.
  • the forms of the "lower limit” and the upper limit disclosed in the “range” of this application may be one or more lower limits and one or more upper limits, respectively.
  • each reaction or operation step may be performed sequentially or not.
  • the reaction methods herein are performed sequentially.
  • a crystalline material having a chemical formula of Na 2 M(C 2 O 4 )X ⁇ nH 2 O, where M is at least one positive divalent metal and X is negative Divalent anion group, and X is not (C 2 O 4 ), 0 ⁇ n ⁇ 12.
  • the above-mentioned crystalline materials are heterogeneous and isomorphic, with a macroscopic hexagonal column shape or a square column shape, and belong to a hexagonal crystal system.
  • the crystalline material has a three-dimensional skeleton structure, in which M, (C 2 O 4 ) and X together constitute the skeleton, and Na ions and water molecules do not participate in the formation of the skeleton.
  • the unit cell includes 3 molecules of planar type [M(C 2 O 4 )], 3 molecules of negative divalent X anion groups, 6 molecules of Na ions, and several free water molecules; of which, negative divalent X anions
  • the group is a bridged anionic group.
  • the schematic diagram of the unit cell microstructure of the Na 2 M(C 2 O 4 )(SO 4 ) ⁇ nH 2 O crystal material includes: every four oxygen atoms Forms a planar oxalate group with two carbon atoms; each M metal atom is connected to the oxalate group through an oxygen bridge bond to form a planar [M(C 2 O 4 )] two-dimensional network plane; the sulfate anion group passes Bridge bonds connect adjacent [M(C 2 O 4 )] two-dimensional network planes to form a three-dimensional skeleton structure; Na ions and water molecules are stabilized in the skeleton voids by electrostatic interaction and hydrogen bonding, respectively.
  • the carbon-oxygen bond length is Carbon-carbon bond length is
  • the metal-oxygen bond is There are 5-7 kinds of atoms nearest to sodium, and the bond length is
  • M is at least one kind of positive divalent metal, which is combined with oxalate to form an extended two-dimensional network plane.
  • the type of M is not limited. It can be one or more positive divalent metal elements, which can meet the structure of crystalline materials. Just change it.
  • X is a negative divalent anion group, and the type of X is not limited, and it is sufficient if the valence of the compound is negative divalent.
  • the X anion group can ensure the electrical neutrality of the overall configuration, which is conducive to the rapid conduction of metal ions (such as Na + ) in the framework structure, and can also ensure the stability of the structure during the redox process.
  • Crystal water in the crystal material does not participate in the formation of the crystal structure, but too much crystal water will affect the stability of the crystal structure.
  • the number n of crystalline water in the crystalline material may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
  • the microscopic three-dimensional skeleton structure of the above crystal has abundant lattice channels for sodium ion migration, provides an effective path for deintercalation and insertion of sodium ions, and provides more active sites for sodium ions.
  • the crystalline material can be used as a positive electrode active material of a sodium ion battery, which greatly improves the sodium insertion performance of the positive electrode active material, and improves the redox potential and structural stability of the positive electrode active material.
  • M is at least one positive divalent transition metal
  • M is at least one of Ti, V, Cr, Mn, Co, Ni, Cu or Zn, or a combination of at least one of the foregoing metals and Fe;
  • X is (SO 4 ), (SeO 4 ), (PO 3 F), (HPO4), (HAsO 4 ), (MoO 4 ), (WO 4 ), (S 2 O 7 ) or (Se 2 O 7 )
  • One of the anionic groups 0 ⁇ n ⁇ 6.
  • M is two or more metals
  • the sum of the moles of various metals is the same as the moles of oxalate ions, and the molar ratio between the various metal elements will not affect the crystal material Structure.
  • the type of metal M can make the structure of the [M(C 2 O 4 )] two-dimensional network plane more stable and provide more abundant sodium ion channels;
  • the type of X and further preferably X are regular tetrahedral anionic groups, It can reduce the space proportion volume of X anion group, provide more space for sodium ion channels, and connect the adjacent [M(C 2 O 4 )] two-dimensional network plane more stably; preferably the number of crystal water can be Significantly reduce the effect of crystal water on the crystal structure.
  • the chemical formula of the preferred crystalline material may be, but not limited to, Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, Na 2 Ni(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, Na 2 Mn( C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, Na 2 Cu(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )( SO 4
  • the tetrahedral anionic group is selected as the bridge connecting the [M(C 2 O 4 )] two-dimensional network plane, which can make the crystalline material provide more abundant channels for the migration of sodium ions. Provide more active sites and improve the sodium intercalation performance and structural stability of crystalline materials.
  • Fig. 2 is a crystal photograph of the crystalline material Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O. It can be seen that the crystalline material has a hexagonal column shape.
  • Fig. 3 is a comparison of the theoretical and experimental XRD spectra of Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O crystal, where the theoretical spectrum is the X-ray diffraction spectrum derived from the single crystal structure. It can be seen from Figure 3 that the peaks of the experimental spectrum and the theoretical spectrum are in good agreement, indicating that the experimental sample has good crystallinity and high purity. In addition, the relative intensity of the diffraction peak is slightly different from the theoretical spectrum, which is caused by the anisotropic growth habit of Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O crystal material.
  • Fig. 4 is a thermogravimetric analysis diagram of Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O crystal. It can be seen from Fig. 4 that when the substance is heated to 180°C, the weight loss reaches 11.03%, corresponding to Two crystal waters are lost; when heating is continued to 310 degrees Celsius, the total weight loss is about 31%, corresponding to the decomposition of Na 2 Co(C 2 O 4 )(SO 4 ) compounds into sodium sulfate and transition metal oxide Co 2 O 3 .
  • a method for preparing the above crystalline material including the following steps: mixing the sodium source, the M source, the oxalate source, the X source and the solvent, and then performing a solvothermal reaction to obtain a crystalline material;
  • the solvent is water
  • the solvothermal reaction is preferably a hydrothermal reaction to prepare crystalline materials.
  • the hydrothermal reaction refers to the use of an aqueous solution as the reaction system in a specific closed reactor (autoclave), heating (or self-rising vapor pressure ), to create a relatively high-temperature and high-pressure reaction environment, so that usually insoluble or insoluble substances are dissolved, and recrystallization is an effective method for inorganic synthesis and material processing.
  • the crystal material obtained after the hydrothermal reaction is visible to the naked eye, and the macroscopic shape is a hexagonal column shape or a square column shape.
  • the order in which the sodium source, the M source, the oxalate source and the X source are added to the solvent can be arbitrarily changed, and the preferred order is to sequentially add the M source, the oxalate source, the sodium source and the X source.
  • the molar ratio of the sodium source, the M source, the oxalate source and the X source is preferably (2-8):1:(1-8):(2-8 );
  • the molar ratio of sodium source, M source, oxalate source and X source can be 2:1:8:2, 3:1:7:3, 4:1:6:4, 5:1:5:5, 6:1:4:6, 7:1:3:7, 8:1:2:8 or 8:1:1:8.
  • Sources of sodium include at least one of oxides, bases or salts containing sodium; sources of sodium include but are not limited to sodium carbonate, sodium acetate, sodium nitrite, sodium fluoroborate, sodium bromide, sodium sulfate, sodium oxalate, persulfate Sodium hydrogen, sodium hydroxide, sodium pyrosulfate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrosulfite, sodium pyrophosphate, sodium chromium sulfate, sodium hydrogen tartrate, sodium dichromate, sodium hydrogen phthalate, hydrogen oxalate
  • the source of M includes at least one of oxides, acids, bases, salts or elements containing M; preferably M is at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, or Combination of at least one of the foregoing metals and Fe.
  • the M source may be one or more of a titanium source, a vanadium source, a chromium source, a manganese source, an iron source, a cobalt source, a nickel source, a copper source, or a zinc source.
  • Titanium sources include but are not limited to elemental titanium, titanium dioxide, titanium dioxide, titanium(III) sulfate, titanium(IV) sulfate, titanium phosphate, sodium fluotitanate, hexafluorotitanic acid, tetrabutyl titanate, tetratitanate Ethyl ester, isopropyl titanate, titanium tetrachloride, titanium trichloride, titanium dihydride, ammonium fluorotitanate, titanium tetrafluoride, titanium dichloride or bis(acetylacetonyl)isopropyl titanate One or more of esters and their hydrates; the preferred source of titanium is one or more of titanium tetrafluoride, titanium (III) sulfate, or titanium trichloride.
  • Vanadium sources include but are not limited to elemental vanadium, vanadium trioxide, vanadium dioxide, vanadium pentoxide, vanadium difluoride, vanadium trifluoride, vanadium tetrafluoride, vanadium pentafluoride, vanadium oxyfluoride, dichloride Vanadium, vanadium trichloride, vanadium tetrachloride, vanadium oxychloride, vanadium dibromide, vanadium tribromide, vanadium tetrabromide, ammonium metavanadate, sodium orthovanadate, sodium metavanadate, vanadium acetylacetonate, One or more of vanadium acetylacetonate, triisopropoxy vanadium oxide or tripropanol vanadium oxide and their hydrates; the preferred source of vanadium is one of vanadium dioxide, vanadium pentoxide or vanadium oxyfluoride or Multiple.
  • Chromium sources include but are not limited to elemental chromium, chromium trioxide, chromium dioxide, chromium trioxide, chromium hydroxide, chromium sulfate, chromite sulfate, lithium chromite, potassium dichromate, sodium dichromate, chromium vanadium , Chromium trifluoride, chromium dichloride, chromium trichloride, chromium bromide, chromium bromide, chromium orthophosphate, chromium metaphosphate, chromium pyrophosphate, chromic acid phosphate, basic chromium phosphate, phosphoric acid One or more of chromium, chromium nitrate, chromium nitrate, chromium formate, cadmium acetate, chromium acetate or chromium oxalate and their hydrates; the preferred source of chromium
  • Manganese sources include but are not limited to elemental manganese, manganese oxide, manganese dioxide, trimanganese tetraoxide, manganese (II) fluoride, manganese (III) fluoride, manganese (II) chloride, manganese (III) chloride, bromine One of manganese chloride, manganese carbonate, manganese nitrate, manganese sulfate, manganese phosphate, manganese dihydrogen phosphate, manganese acetylacetonate, manganese formate, manganese (II) acetate, manganese (III) acetate or manganese oxalate and their hydrates or Multiple; preferably, the source of manganese is one or more of manganese acetate, manganese oxalate or manganese chloride.
  • Cobalt sources include but are not limited to elemental cobalt, cobalt monoxide, cobalt trioxide, tricobalt tetroxide, cobalt (II) hydroxide, cobalt (III) hydroxide, cobalt (II) fluoride, cobalt (III) fluoride, chloride
  • the source of cobalt is one or more of cobalt acetate, cobalt oxalate or cobalt chloride.
  • Nickel sources include but are not limited to elemental nickel, nickel oxide, high nickel oxide, nickel hydroxide, high nickel hydroxide, nickel fluoride, nickel chloride, nickel bromide, nickel nitrate, nickel carbonate, nickel sulfate, nickel acetate, oxalic acid Nickel, nickel bis(hexafluoroethylacetone), nickel sulfamate, basic nickel carbonate, nickel acetylacetonate dihydrate, nickel trifluoromethanesulfonate, nickel benzenesulfonate, nickel acetylacetonate or nickel fluoroborate and One or more of its hydrates; preferably, the nickel source is one or more of nickel oxalate, nickel chloride, nickel fluoride, or nickel acetate.
  • Copper sources include but are not limited to elemental copper, cuprous oxide, copper oxide, copper hydroxide, copper fluoride, copper chloride, copper bromide, copper carbonate, basic copper carbonate, copper nitrate, copper sulfate, copper acetate, oxalic acid
  • the preferred copper source is one of copper acetate, copper sulfate or copper chloride or Multiple.
  • Zinc sources include but are not limited to elemental zinc, zinc oxide, zinc hydroxide, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, zinc carbonate, zinc acetate, zinc oxalate, zinc citrate , Zinc fluoroborate, zinc tartrate, zinc borate, zinc metaborate, zinc acetylacetonate or zinc gluconate and one or more of their hydrates; the preferred zinc source is one or both of zinc sulfate or zinc chloride Species.
  • Iron sources include but are not limited to elemental iron, ferric oxide, ferric oxide, ferrous hydroxide, ferric hydroxide, ferrous fluoride, ferric fluoride, ferrous chloride, ferric chloride, ferrous bromide , Iron bromide, iron formate, ferrous acetate, ferrous nitrate, ferrous sulfate, ferric nitrate, ferric sulfate, ferric acetylacetonate, one or more of ferrous oxalate, ferric oxalate and their hydrates; preferably iron The source is one or more of ferrous oxalate, ferrous chloride and their hydrates.
  • the oxalate source includes at least one of oxalate-containing acids or salts; oxalate source includes but is not limited to one or more of oxalic acid, sodium oxalate, sodium hydrogen oxalate, ammonium oxalate, or diethyl oxalate, and hydrates thereof; Oxalic acid and its hydrates are preferred.
  • the source of X is a source of a negative dianion group, and may be, but not limited to, at least one of X-containing acids or salts.
  • X is (SO 4 ), (SeO 4 ), (PO 3 F), (HPO4), (HAsO 4 ), (MoO 4 ), (WO 4 ), (S 2 O 7 ) or (Se 2 O 7 )
  • SO 4 SO 4
  • SeO 4 PO 3 F
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HPO4 HPO4
  • HSO 4 HPO 4
  • HPO4 HPO4
  • the X source may be one of a sulfate source, a selenate source, a fluoride phosphate source, a monohydrogen phosphate source, a monohydroarsenate source, a molybdate source, a tungstate source, a pyrosulfate source, or a pyroselenate source. .
  • Sources of sulfate include, but are not limited to, one or more of sulfuric anhydride, sulfuric acid solution, alkali metal sulfate, alkaline earth metal sulfate, ammonium sulfate, ammonium bisulfate, or desired transition metal sulfate; preferably sulfuric acid and sodium sulfate One or two.
  • Sources of selenate include, but are not limited to, one or more of selenic anhydride, selenic acid, alkali metal selenate, alkaline earth metal selenate, ammonium selenate, ammonium hydrogen selenate, or desired transition metal selenate; preferably One or both of selenic acid and sodium selenate.
  • Sources of fluorinated phosphate include, but are not limited to, one or more of fluorinated phosphoric acid, lithium fluorinated phosphate, sodium fluorinated phosphate, potassium fluorinated phosphate, ammonium fluorinated phosphate, or rubidium fluorinated phosphate; preferably fluorinated phosphoric acid and fluorine One or two of sodium phosphate.
  • Sources of monohydrogen phosphate include, but are not limited to, one or more of phosphoric anhydride, phosphoric acid, alkali metal monohydrogen phosphate, alkaline earth metal monohydrogen phosphate, or the desired transition metal monohydrogen phosphate; preferably sodium monohydrogen phosphate and transition One or two of the metal phosphates.
  • Sources of monohydroarsenic acid include, but are not limited to, one or more of arsenic anhydride, arsenic acid solution, alkali metal arsenate, alkaline earth metal arsenate, ammonium arsenate, ammonium hydrogen arsenate, or desired transition metal arsenate It is preferably one or both of arsenic acid and sodium arsenate.
  • Molybdate sources include, but are not limited to, molybdenum trioxide, molybdenum trioxide, molybdic acid solution, alkali metal molybdate, alkaline earth metal molybdate, ammonium molybdate, ammonium hydrogen molybdate, or the desired transition metal molybdate.
  • molybdic acid and sodium molybdate One or more; preferably one or two of molybdic acid and sodium molybdate.
  • Tungstic acid sources include, but are not limited to, one or more of tungstic anhydride, tungstic acid solution, alkali metal tungstate, alkaline earth metal tungstate, ammonium tungstate, ammonium hydrogen tungstate, or desired transition metal tungstate; One or both of tungstic acid and sodium tungstate are preferred.
  • Sources of pyrosulfate include, but are not limited to, one or more of pyrosulfuric anhydride, pyrosulfuric acid solution, alkali metal pyrosulfate, alkaline earth metal pyrosulfate, ammonium pyrosulfate, ammonium pyrosulfate, or desired transition metal pyrosulfate ; Preferably one or both of pyrosulfuric acid and sodium pyrosulfate.
  • Pyroselenate sources include, but are not limited to, pyroselenic acid anhydride, pyroselenic acid solution, alkali metal pyroselenate, alkaline earth metal pyroselenate, ammonium pyroselenate, ammonium pyroselenate, or desired transition metal pyroselenate One or more of them; preferably one or both of pyroselenic acid and sodium pyroselenate.
  • the hydrates of the compounds that provide the sodium source, the M source, the oxalate source, and the X anion source can also be used as raw material sources for hydrothermal synthesis, and the hydrates will not affect the prepared crystal structure.
  • the above solvent is at least one of water, alcohols, ketones or pyridines; preferred solvents include but are not limited to one or more of water, methanol, ethanol, acetone, ethylene glycol or pyridine, preferably water.
  • the temperature of the solvothermal reaction is 100-300°C and the time is 4-100h; the temperature of the solvothermal reaction is 180-220°C and the time is 48-72h.
  • the temperature of the solvothermal reaction is typically, but not limited to, for example, 100°C, 130°C, 150°C, 180°C, 200°C, 230°C, 270°C, or 300°C; the time of the solvothermal reaction is typical, but not limited to, for example: 4h, 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h or 100h.
  • An exemplary method for preparing a crystalline material includes the following steps:
  • step (a) is not particularly limited, as long as a uniform mixed solution can be obtained after mixing.
  • the exemplary method for preparing a crystalline material defines the process parameters of the manufacturing process, and clearly shows the sequence relationship of each process step. According to this exemplary method, the preparation process time can be shortened, and a crystal material with better purity can be obtained.
  • the use of the above-mentioned crystalline material in preparing a positive electrode active material is provided.
  • the three-dimensional skeleton structure has abundant lattice channels for the migration of sodium ions, provides an effective sodium ion deintercalation and embedded diffusion path, and provides more active sites for sodium ions Point, so this crystalline material can be used as a positive electrode active material for sodium ion batteries.
  • the positive electrode active material used in the sodium ion battery needs to be used after grinding, preferably after grinding
  • the particle size is 100-2000nm. Grinding the crystalline material and preferably the particle size after grinding can increase its contact area with the electrolyte and provide more active sites for sodium ions.
  • a sodium ion battery cathode material including a cathode active material, a cathode conductive agent and a cathode binder; the weight ratio of the cathode active material, the cathode conductive agent and the cathode binder is ( 60-90): (5-30): (3-10); the positive electrode active material is the above-mentioned crystalline material.
  • the weight ratio of the positive electrode active material, the positive electrode conductive agent and the positive electrode binder are typical but non-limiting examples are, for example, 60:30:10, 65:25:10, 70:23:7, 75:17:8, 80:10 :10, 85:6:9 or 90:5:10.
  • the conductive agent is to ensure that the electrode has good conductivity.
  • a certain amount of conductive material is usually added to collect micro-current between the active material and the active material and the current collector to reduce the electrode.
  • the contact resistance accelerates the moving rate of electrons, and can also effectively increase the migration rate of sodium ions in the electrode material, thereby improving the charge and discharge efficiency of the electrode.
  • the positive electrode conductive agent may be, but not limited to, at least one of conductive carbon black, conductive carbon spheres, conductive graphite, conductive carbon fiber, carbon nanotubes, graphene, or reduced graphene oxide.
  • the binder can ensure that the battery has a certain bonding strength between the active material particles and between the active particles and the current collector during the use of the battery, and it is conducive to the formation of the SEI film and improves the cycle performance and service life of the electrode.
  • the positive electrode binder may be, but not limited to, at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber (SBR), or polyolefins.
  • the weight ratio of the positive electrode active material, the positive electrode conductive agent and the positive electrode binder, and the types of the positive electrode conductive agent and the positive electrode binder used are good for the positive electrode active material to adhere well to the current collector and improve the charge and discharge of the positive electrode The efficiency improves the electrochemical performance of the prepared cathode material of sodium ion batteries.
  • the sodium ion battery positive electrode material As the positive electrode active material of the sodium ion battery positive electrode material, the sodium ion battery positive electrode material has the same advantages as the above crystalline material and the above positive electrode active material, the sodium ion battery positive electrode material has high sodium insertion performance, high redox potential, The advantages of good cycle stability and low cost.
  • a sodium ion battery including the foregoing positive electrode material for sodium ion batteries.
  • the shape of the sodium ion battery may be, but not limited to, a button battery, a flat battery, or a cylindrical battery.
  • the working principle of sodium ion batteries is similar to that of lithium ion batteries.
  • the specific capacity of the negative electrode of the sodium ion battery should be higher than that of the positive electrode, so that the positive electrode material determines the capacity of the sodium ion battery.
  • the positive electrode active material provided in the present application or the positive electrode material of a sodium ion battery is used as a positive electrode, so that the sodium ion battery has the advantages of large battery capacity, good cycle stability and low cost.
  • the sodium ion battery further includes a negative electrode material, a negative electrode current collector, a positive electrode current collector, an electrolyte, and a separator.
  • the negative electrode material includes a negative electrode active material, a negative electrode conductive agent and a negative electrode binder, and the weight ratio of the negative electrode active material, negative electrode conductive agent and negative electrode binder is (60-90):(5- 30): (3-10);
  • the negative electrode active material may be, but not limited to, at least one of carbon materials, metals, alloys, sulfides, nitrides, oxides, or carbides.
  • the negative electrode conductive agent may be, but not limited to, at least one of conductive carbon black, conductive carbon balls, conductive graphite, conductive carbon fiber, carbon nanotubes, graphene, or reduced graphene oxide; preferably, the negative electrode binder may be, but not limited to At least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber, or polyolefin.
  • the materials of the negative electrode current collector and the positive electrode current collector independently include one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, or germanium, or an alloy of the above metals Or composite materials of the above metals;
  • the negative electrode conductive agent, the negative electrode binder and the added amount thereof are preferred, which is favorable for the negative electrode active material to adhere well to the negative electrode current collector and improve the charge and discharge efficiency of the negative electrode.
  • the electrolyte includes an electrolyte and an electrolyte solvent; the electrolyte is a sodium salt.
  • the molar concentration of sodium salt in the electrolyte is 0.1-10mol/L, and the molar concentration of sodium salt is typically, but not limited to, for example, 0.1mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L , 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L.
  • the sodium salt as the electrolyte is not particularly limited as long as it can be dissociated into cations and anions.
  • the sodium salt may be, but not limited to, sodium perchlorate, sodium hexafluorophosphate, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate borate, sodium pyrophosphate, dodecane Sodium benzenesulfonate, sodium dodecyl sulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodide, sodium iodide, silicon Sodium, sodium lignosulfonate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium t
  • the electrolyte solvent is not particularly limited, as long as the electrolyte solvent can dissociate the electrolyte into cations and anions, and the cations and anions can freely migrate.
  • Preferred solvents include one or more of esters, sulfones, ethers or nitriles; specifically, the solvent may be, but not limited to, propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate ( DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate Ester (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), ⁇ -butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF) , 1,
  • the electrolyte solvent and the sodium salt can dissolve the sodium salt better and make the sodium ion freely move more conveniently.
  • the sodium salt concentration in the electrolyte is too low, the ion transmission performance is poor, and the conductivity is low; the sodium salt concentration is too high, too many ions, the viscosity of the electrolyte and the degree of ion association will also increase with the increase of the sodium salt concentration, which It will also reduce the electrical conductivity.
  • the molar concentration of sodium salt is preferred to avoid the effects caused by too low or too high sodium salt concentration.
  • the electrolyte further includes additives; the mass fraction of the additives in the electrolyte is 0.1-20%.
  • Typical but non-limiting examples of the mass fraction of additives are 0.1%, 1%, 5%, 8%, 10%, 12%, 14%, 16%, 18% or 20%.
  • Additives added in the electrolyte can form a stable solid electrolyte membrane on the surface of the negative electrode current collector, increasing the service life of the battery.
  • Additives include but are not limited to one or more of esters, sulfones, ethers, nitriles or olefins.
  • the additives may be, but not limited to, fluoroethylene carbonate, vinylene carbonate, ethylene ethylene carbonate, 1,3-propane sultone, 1,4-butane sultone, vinyl sulfate, Propylene sulfate, ethylene sulfate, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide , Anisole, acetamide, diazabenzene, m-diazepine, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluoroanisole, fluorochain ether, difluoro Ethylene methyl carbonate, trifluoromethyl ethylene carbonate, chloroethylene carbonate, brominated ethylene carbonate, trifluoroethylphosphonic acid, bromobutyrolactone, fluoro
  • Preferred separators include but are not limited to insulating porous polymer films or inorganic porous films.
  • the separators include but are not limited to one or more of porous polypropylene films, porous polyethylene films, fiberglass paper or porous ceramic separators.
  • the material of the separator can reduce the internal resistance of the battery and increase the cycle life of the battery.
  • An exemplary method for preparing a sodium ion battery includes the following steps:
  • steps (a)-(d) describe the operations of the sodium ion battery preparation method in a specific order, it is not required or implied that these operations must be performed in this specific order, steps (a), ( The preparation of b), (c) and (d) can be performed simultaneously or in any order.
  • the sodium ion battery prepared according to the preparation method of the sodium ion battery has all the effects of the foregoing sodium ion battery, and will not be repeated here.
  • a device including a sodium ion battery is provided.
  • devices including the above-mentioned sodium ion battery such as portable electronic equipment, electrical equipment, and power tools, have the same advantages as the above-mentioned sodium ion battery.
  • the preparation method includes the following steps:
  • a crystalline material with the chemical formula Na 2 Ni(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O the raw materials used in the preparation method are 0.852g Na 2 SO 4 , 0.283g NiCl 2 ⁇ 6H 2 O and 0.378 g H 2 C 2 O 4 ⁇ 2H 2 O, the rest is the same as in Example 1.
  • a crystalline material the chemical formula is Na 2 Mn(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O
  • the raw materials used in the preparation method are Na 2 SO 4 , MnC 2 O 4 ⁇ 2H 2 O and H 2 C 2 O 4 ⁇ 2H 2 O
  • the molar ratio is 6:1:2.5, the rest is the same as in Example 1.
  • a crystalline material the chemical formula is Na 2 Cu(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O
  • the raw materials used in the preparation method are Na 2 SO 4 , CuSO 4 and H 2 C 2 O 4 ⁇ 2H 2 O
  • the molar ratio is 6:1:3.5
  • the rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ⁇ 2H 2 O, MnC 2 O 4 .2H 2 O and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.5:0.5:3.5, the rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ⁇ 2H 2 O, MnC 2 O 4 .2H 2 O and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.75:0.25:3.5, the rest is the same as Example 1.
  • a crystalline material with the chemical formula Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ⁇ 2H 2 O, MnC 2 O 4 .2H 2 O and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.9:0.1:3.5, the rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ⁇ 2H 2 O, Ti 2 (SO 4 ) 3 and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.9:0.1:3.5, the rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ⁇ 2H 2 O, VO 2 and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.9:0.1:3.5, the reaction temperature is 220° C. The rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ⁇ 2H 2 O, ZnSO 4 and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.9:0.1:3.5, the reaction temperature is 180° C. The rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ⁇ 2H 2 O, CuSO 4 and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.9:0.1:4, the reaction temperature is 180° C. The rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O The raw materials used in the preparation method are Na 2 SO 4 and Ti 2 (SO 4 ) 3 , FeC 2 O 4 ⁇ 2H 2 O, MnC 2 O 4 ⁇ 2H 2 O and H 2 C 2 O 4 ⁇ 2H 2 O, and the molar ratio is 8:0.1:0.8:0.1:3, the reaction temperature is 190 °C, The rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O The raw materials used in the preparation method are Na 2 SO 4 , NiCl 2 ⁇ 6H 2 O, MnC 2 O 4 ⁇ 2H 2 O, CoC 2 O 4 ⁇ 2H 2 O and H 2 C 2 O 4 ⁇ 2H 2 O, and the molar ratio is 4:0.6:0.2:0.2:2, the reaction temperature is 210 °C, the rest Same as Example 1.
  • a crystalline material the chemical formula is Na 2 V 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O
  • the raw materials used in the preparation method are Na 2 SO 4 , VO 2 , FeC 2 O 4 ⁇ 2H 2 O, MnC 2 O 4 ⁇ 2H 2 O and H 2 C 2 O 4 ⁇ 2H 2 O
  • the molar ratio is 4:0.1:0.8:0.1:3
  • the reaction temperature is 220 °C
  • the rest is the same as Example 1 the same.
  • a crystalline material the chemical formula is Na 2 V 0.2 Fe 0.7 Mn 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O
  • the raw materials used in the preparation method are Na 2 SO 4 , VO 2 , FeC 2 O 4 ⁇ 2H 2 O, MnC 2 O 4 ⁇ 2H 2 O and H 2 C 2 O 4 ⁇ 2H 2 O
  • the molar ratio is 6:0.2:0.7:0.1:3.5
  • the reaction temperature is 180 °C
  • the rest is the same as Example 1 the same.
  • a crystalline material the chemical formula is Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 6H 2 O, the water solvent used in the preparation method is 5 mL, the reaction temperature is 100° C, and the rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Co(C 2 O 4 )(SeO 4 ) ⁇ 4H 2 O is used instead of sodium sulfate, the water solvent used is 5 mL, and the reaction temperature is At 120°C, the rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Co(C 2 O 4 )(WO 4 ) ⁇ 6H 2 O the raw materials used in the preparation method are Na 2 WO 4 , CoC 2 O 4 ⁇ 2H 2 O, H 2 C 2 O 4 ⁇ 2H 2 O, and the molar ratio is 6:1:4, the reaction temperature is 180°C, and the rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Co(C 2 O 4 )(S 2 O 7 ) ⁇ 2H 2 O The raw materials used in the preparation method are Na 2 S 2 O 7 and CoC 2 O 4 ⁇ 2H 2 O , H 2 C 2 O 4 ⁇ 2H 2 O, and the molar ratio is 3.5:1:4, the reaction temperature is 150 °C, the solvent used is 2mL of absolute ethanol, the rest is the same as in Example 1.
  • a crystalline material with the chemical formula Na 2 Co(C 2 O 4 )(HPO 4 ) ⁇ 2H 2 O the raw materials used in the preparation method are Na 2 HPO 4 , CoC 2 O 4 ⁇ 2H 2 O, H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4.5:1:4, the reaction temperature is 180° C., the solvent used is 2 mL of absolute ethanol, and the rest is the same as in Example 1.
  • the positive electrode active material is a crystalline material, the chemical formula is Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O, and the particle size is 500 nm;
  • the preparation method of the above sodium ion half-cell includes the following steps:
  • the glass fiber film is cut into 16mm diameter discs and used as a diaphragm for backup;
  • Battery assembly In an inert gas-protected glove box, the above-prepared battery positive electrode, separator and battery negative electrode are closely stacked in sequence, and the electrolyte is added dropwise to completely infiltrate the separator, and then the above-mentioned stacked part is packaged into a button battery Case, complete battery assembly.
  • Example 22 Na 2 Co(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Natural graphite
  • Example 23 Na 2 Ni(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O
  • Soft carbon Example 24
  • Spherical graphite Example 25 Na 2 Cu(C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Na 2 Ti 8 O 17
  • Example 26 Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Na
  • Example 27 Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Na
  • Example 28 Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Na
  • Example 29 Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Na
  • Example 30 Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Na
  • Example 31 Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Na
  • Example 32 Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Na
  • Example 33 Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Na
  • Example 34 Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 ) ⁇ 2H 2 O Na
  • Example 35 Na
  • the above examples 22-41 respectively use the crystalline materials provided in examples 1-20, and the particle size is 500 nm.
  • the preparation method of the sodium ion full battery provided in the above embodiments 22-41 includes the following steps:
  • the glass fiber film is cut into 16mm diameter discs and used as a diaphragm for backup;
  • Battery assembly In an inert gas-protected glove box, the above-prepared battery positive electrode, separator and battery negative electrode are closely stacked in sequence, and the electrolyte is added dropwise to completely infiltrate the separator, and then the above-mentioned stacked part is packaged into a button battery Case, complete battery assembly.
  • a sodium ion full battery is different from Example 22 in that the particle size of the positive electrode crystal material is 1000 nm.
  • Example 22 is the difference equimolar amount of crystalline material CoCl 2 Alternative preparation of CoC 2 O 4 ⁇ 2H 2 O.
  • Example 22 A sodium ion full battery, the difference from Example 22 is that MCMB replaces natural graphite.
  • a sodium ion full battery is different from Example 22 in that the positive electrode active material is NaCoO 2 .
  • a sodium ion full battery differs from Example 22 in that the positive electrode active material is Na 3 V 2 (PO 4 ) 3 .
  • a sodium ion full battery differs from Example 22 in that the cathode active material is Na 2 C 6 H 2 O 4 .
  • Example 21 The sodium ion half-cell of Example 21 was subjected to a cycle performance test, and the charge-discharge voltage range was 2.0V-4.5V, and the charge-discharge current was 100mA/g. 5 is a graph showing the relationship between the specific charge capacity, specific discharge capacity, and Coulomb efficiency under different cycle times of the sodium ion battery of Example 21.
  • the first coulombic efficiency of the sodium ion battery of Example 21 is 88%, the reversibility of charge and discharge is good, and the cycle stability is good.
  • the test method is as follows:
  • Constant current 1C
  • protection condition cut-off voltage ⁇ 4.5V
  • Constant current 1C
  • protection condition cut-off voltage ⁇ 1.5V
  • the number of stable cycles refers to the number of cycles that can be cycled while maintaining 80% of the initial battery capacity.
  • Example 29 1.7-4.3 0.87 160
  • Example 30 1.5-4.0 0.98 130
  • Example 31 1.5-4.2 1.02 80
  • Example 32 1.5-4.2 0.64 80
  • Example 33 1.5-4.2 1.13 100
  • Example 34 3.0-4.5 1.75 150
  • Example 35 1.5-4.0 1.24
  • Example 36 1.5-4.0 1.65 90
  • Example 37 1.5-4.0 0.75 130
  • Example 38 1.5-4.0 0.69 130
  • Example 39 2.5-4.5 0.72
  • Example 40 2.5-4.5 0.56
  • Example 41 2.5-4.5 1.08 150
  • Example 42 1.7-4.3 1.03 130
  • Example 43 1.5-4.0 1.32
  • Example 44 1.5-4.0 1.15 250 Comparative Example 1 3.0-4.5 1.65 50 Comparative Example 2 1.5-4.2 1.56 150 Comparative Example 3 1.0-3.0 0.45 30
  • the positive electrode active material of the sodium ion battery provided in this application adopts the chemical formula Na 2 M(C 2 O 4 )X ⁇ nH 2 O (where M is at least one positive divalent metal and X is negative divalent)
  • the valence anion group, 0 ⁇ n ⁇ 12) crystalline materials through the coordination of the positive and negative materials, the resulting sodium ion full battery has a higher operating voltage, battery capacity and good cycle stability.
  • Example 34 The difference between Examples 26-33 and Example 34 is the type and content of metal M in the positive electrode active material.
  • the working voltage and battery capacity of the sodium ion battery provided in Example 34 are higher than those provided in Examples 26-33 Batteries, and the stable cycle number of Example 34 is also high, which indicates that the type and content of the M metal element in the crystalline material as the positive electrode active material will affect the electrochemical performance of the sodium ion battery.
  • Example 35 and 36 The difference between Examples 35 and 36 and Example 22 is that the positive electrode active material is different, the electrochemical performance of the obtained sodium ion battery is different, and the working voltage, battery capacity and number of stable cycles are different.
  • the sodium ion battery provided by Example 22 has the highest cycle performance stability, and the working voltage and battery capacity of the sodium ion battery provided by Example 22 and Examples 35 and 36 are not much different.
  • Example 37 and Example 22 The difference between Example 37 and Example 22 is that the positive electrode active material has different crystal water content; the difference between Examples 38 and 39 and Example 22 is that the positive electrode active material has different cathode ion groups and crystal water content; Example 40, The difference between 41 and Example 22 is that the cathode ion group of the positive electrode active material is different; the electrochemical performance of the sodium ion battery of Example 22 is better than the sodium ion batteries of Examples 37-41, which shows that the crystalline water of the positive electrode active material The content and the type of anionic groups will affect the electrochemical performance of sodium ion batteries.
  • Example 42 and Example 22 is the particle size of the positive electrode active material; the difference between Example 43 and Example 22 is the different cobalt source for preparing the positive electrode active material; the difference between Example 44 and Example 22 is the negative electrode active material .
  • the working voltage, battery capacity, and stable cycle number of Example 22 are slightly higher than those of Example 42; the working voltage, battery capacity, and stable cycle number of Example 22 are not significantly different from those of Examples 43 and 43, indicating positive electrode activity
  • the particle size of the material, the raw material containing metal M and the negative electrode active material have an effect on the electrochemical performance of the sodium ion battery, but it is not significant.
  • Comparative Example 1 and Example 22 The difference between Comparative Example 1 and Example 22 is that the positive electrode active material is a layered oxide containing sodium and cobalt; the difference between Comparative Example 2 and Example 22 is that the positive electrode active material is an existing polyanion compound; The difference between Ratio 3 and Example 22 is that the positive electrode active material is an existing organic positive electrode material.
  • the sodium-ion batteries of Comparative Examples 1-3 are obviously not as stable as those of Example 22, and the working voltage and battery capacity of the sodium-ion batteries of Comparative Examples 1 and 2 are not significantly different from that of Example 22, Comparative Example 3
  • the operating voltage and battery capacity of the sodium ion battery are significantly lower than the sodium ion battery of Example 22. This shows that the structural stability of the positive electrode active material prepared by the crystalline material provided in the present application is higher than that of the comparative example.

Abstract

The present application discloses a crystal material, a preparation method and a use thereof, a positive electrode material for a sodium ion battery, a sodium ion battery, and an apparatus, relating to the technical field of sodium ion batteries. The crystal material is represented by a chemical formula of Na2M(C2O4)X·nH2O, where M is at least one positive divalent metal, X is a negative divalent anionic group, and X is not (C2O4), 0≤n≤12. The crystal material belongs to a hexagonal crystal system and has a three-dimensional skeleton structure. Sodium ions and water molecules do not participate in the construction of the skeleton. The crystal material has an excellent charge-discharge specific capacity and a high redox potential, and can significantly improve the structural stability of a positive electrode active material. This application resolves the defects of a complex preparation process, high costs, and unsatisfactory stability of existing positive electrode material for sodium ion batteries. The positive electrode material for a sodium ion battery provided by the present application has the advantages of high sodium insertion performance, high redox potential, excellent cycle stability, and low costs.

Description

晶体材料及其制备方法和用途、钠离子电池正极材料、钠离子电池和设备Crystal material and its preparation method and use, anode material for sodium ion battery, sodium ion battery and equipment 技术领域Technical field
本申请涉及钠离子电池技术领域，具体而言，涉及一种晶体材料及其制备方法和用途、钠离子电池正极材料、钠离子电池和设备。The present application relates to the technical field of sodium ion batteries, in particular, to a crystalline material and its preparation method and use, positive electrode materials for sodium ion batteries, sodium ion batteries and equipment.
背景技术Background technique
二次电池也称为可充电电池，是一种可重复充放电和循环使用的电池。锂离子电池是二次电池中应用较广的，其具有能量密度高和寿命长的优点，在储能领域有着广泛的应用，但锂的自然丰度低且分布不均，使得锂离子电池成本日益增高。钠在元素周期表中位于锂的正下方，具与锂有相似的化学性质，且地壳中储量丰富，其丰度约为锂的1000倍，所以钠离子电池有望弥补锂离子电池的不足，成为新一代高性能和低成本储能技术。钠离子电池的工作原理与锂离子电池相似，通过钠离子在正负极发生氧化还原反应实现能量的存储与释放。钠离子电池的核心组成部件包含正极、负极和电解液。充电时，钠离子从正极活性材料中脱出，嵌入负极活性材料；放电时，钠离子从负极活性材料脱出而嵌入到正极活性材料中。为了避免金属钠在负极析出，钠离子电池负极设计容量应高于正极，使得正极材料决定了钠离子电池容量。此外，钠离子电池电压为正负极材料电势差，氧化还原电势越高的正极材料越有利于获得高的钠离子电池电压。正极材料的结构稳定性是目前钠离子电池发展的主要瓶颈。The secondary battery is also called a rechargeable battery, and is a battery that can be repeatedly charged and discharged and recycled. Lithium-ion batteries are widely used in secondary batteries. They have the advantages of high energy density and long life. They have a wide range of applications in the field of energy storage, but the low natural abundance and uneven distribution of lithium make lithium-ion batteries cost. Increasing day by day. Sodium is located directly below lithium in the periodic table, and has similar chemical properties to lithium, and the crust is rich in reserves, and its abundance is about 1000 times that of lithium, so sodium ion batteries are expected to make up for the shortcomings of lithium ion batteries. A new generation of high-performance and low-cost energy storage technology. The working principle of a sodium ion battery is similar to that of a lithium ion battery, and energy storage and release are realized through the redox reaction of sodium ions at the positive and negative electrodes. The core components of sodium ion battery include positive electrode, negative electrode and electrolyte. During charging, sodium ions are extracted from the positive electrode active material and embedded in the negative electrode active material; during discharge, sodium ions are extracted from the negative electrode active material and embedded in the positive electrode active material. In order to avoid the precipitation of metallic sodium in the negative electrode, the design capacity of the negative electrode of the sodium ion battery should be higher than that of the positive electrode, so that the positive electrode material determines the capacity of the sodium ion battery. In addition, the voltage of the sodium ion battery is the potential difference between the positive and negative electrode materials, and the higher the redox potential of the positive electrode material, the more favorable it is to obtain a high sodium ion battery voltage. The structural stability of the cathode material is currently the main bottleneck in the development of sodium ion batteries.
钠离子电池正极材料可大致分为层状氧化物、聚阴离子化合物和有机正极。现阶段钠离子电池正极材料种类有限，且电化学性能不够理想且制备工艺较为复杂。层状氧化物正极材料理论比容量较高，但是高电压易触发不可逆释氧，使电池失效。有机正极材料存在着工作电压低和热稳定性差的问题。相较之下，聚阴离子化合物结构稳定，其聚阴离子基团能够通过诱导作用调节材料电化学反应电位，因而拥有优良的应用前景。但是现阶段钠离子电池聚阴离子正极材料的研究较少，且主要集中在磷酸盐和硫酸盐体系，其制备工艺复杂、成本高和性能不够理想。The positive electrode material of sodium ion battery can be roughly divided into layered oxide, polyanion compound and organic positive electrode. At present, the types of anode materials for sodium ion batteries are limited, and the electrochemical performance is not ideal and the preparation process is relatively complicated. The theoretical specific capacity of the layered oxide cathode material is relatively high, but high voltage can easily trigger irreversible oxygen release, which can cause battery failure. Organic cathode materials have the problems of low operating voltage and poor thermal stability. In contrast, the polyanionic compound has a stable structure, and its polyanionic group can adjust the electrochemical reaction potential of the material through induction, and thus has excellent application prospects. However, there are few studies on polyanion cathode materials for sodium ion batteries at this stage, and they are mainly concentrated in phosphate and sulfate systems. Their preparation process is complicated, the cost is high and the performance is not ideal.
有鉴于此，特提出本申请以解决上述技术问题中的至少一个。In view of this, this application is specifically filed to solve at least one of the above technical problems.
发明内容Summary of the invention
本申请的第一目的在于提供一种晶体材料，该晶体材料属于异质同构，六方晶系，具有微观三维的骨架结构，其中钠离子和水分子不参与骨架的构成，晶体结构中具有丰富的孔道供钠离子迁移。该晶体材料可以用于钠离子电池的正极活性材料，使包含其的正极活性材料的嵌钠性能大幅度提升，提高正极活性材料的氧化还原电势和结构稳定性。The first object of the present application is to provide a crystalline material, which is a heterogeneous, hexagonal crystal system with a microscopic three-dimensional skeleton structure, in which sodium ions and water molecules do not participate in the formation of the skeleton, the crystal structure is rich in The holes are used for sodium ion migration. The crystalline material can be used as a positive electrode active material of a sodium ion battery, which greatly improves the sodium insertion performance of the positive electrode active material containing the same, and improves the redox potential and structural stability of the positive electrode active material.
本申请的第二目的在于提供一种晶体材料的制备方法，该制备方法采用溶剂热合成晶体，工艺简单，成本低廉，适于工业化生产。The second object of the present application is to provide a method for preparing a crystalline material. The preparation method uses solvothermal synthesis of crystals, which has a simple process and low cost, and is suitable for industrial production.
本申请的第三目的在于提供上述晶体材料或上述晶体材料的制备方法制备得到的晶体材料在制备正极活性材料中的应用。The third object of the present application is to provide the application of the above-mentioned crystal material or the above-mentioned crystal material preparation method to the preparation of a positive electrode active material.
本申请的第四目的在于提供一种钠离子电池正极材料，包含上述晶体材料，或晶体材料的制备方法制备得到的晶体材料。The fourth object of the present application is to provide a positive electrode material for a sodium ion battery, comprising the above crystalline material, or the crystalline material prepared by the method for preparing the crystalline material.
本申请的第五目的在于提供一种钠离子电池，包括上述的钠离子电池正极材料，该钠离子电池具有与上述晶体材料或钠离子正极活性材料相同的优势。The fifth object of the present application is to provide a sodium ion battery including the above-mentioned sodium ion battery cathode material, which has the same advantages as the above-mentioned crystalline material or sodium ion cathode active material.
本申请的第六目的在于提供一种包括钠离子电池的设备。The sixth object of the present application is to provide a device including a sodium ion battery.
为了实现本申请的上述目的，特采用以下技术方案：In order to achieve the above purpose of this application, the following technical solutions are specifically adopted:
第一方面，本申请提供了一种晶体材料，晶体材料的化学式为Na 2M(C 2O 4)X·nH 2O，其中M为至少 一种正二价金属，X为负二价阴离子基团，且X不为(C 2O 4)，0≤n≤12； In the first aspect, the present application provides a crystalline material with a chemical formula of Na 2 M(C 2 O 4 )X·nH 2 O, where M is at least one positive divalent metal and X is a negative divalent anion group Group, and X is not (C 2 O 4 ), 0≤n≤12;
进一步，在本申请提供的技术方案的基础上，所述M为至少一种正二价过渡金属；Further, on the basis of the technical solution provided by the present application, the M is at least one positive divalent transition metal;
优选地，所述M为Ti、V、Cr、Mn、Co、Ni、Cu或Zn中的至少一种，或前述至少一种金属与Fe的组合；Preferably, the M is at least one of Ti, V, Cr, Mn, Co, Ni, Cu or Zn, or a combination of at least one of the foregoing metals and Fe;
优选地，所述X为(SO 4)、(SeO 4)、(PO 3F)、(HPO4)、(HAsO 4)、(MoO 4)、(WO 4)、(S 2O 7)或(Se 2O 7)阴离子基团中的一种，0≤n≤6； Preferably, X is (SO 4 ), (SeO 4 ), (PO 3 F), (HPO4), (HAsO 4 ), (MoO 4 ), (WO 4 ), (S 2 O 7 ) or ( Se 2 O 7 ) one of the anionic groups, 0≤n≤6;
优选地，所述晶体材料的化学式为Na 2Co(C 2O 4)(SO 4)·2H 2O、Na 2Ni(C 2O 4)(SO 4)·2H 2O、Na 2Mn(C 2O 4)(SO 4)·2H 2O、Na 2Cu(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.5Mn 0.5(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.75Mn 0.25(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Ti 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9V 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Zn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Cu 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Ti 0.1Fe 0.8Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Ni 0.6Mn 0.2Co 0.2(C 2O 4)(SO 4)·2H 2O、Na 2V 0.1Fe 0.8Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2V 0.2Fe 0.7Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Co(C 2O 4)(SO 4)·6H 2O、Na 2Co(C 2O 4)(SeO 4)·2H 2O、Na 2Fe(C 2O 4)(SeO 4)·4H 2O、Na 2Fe(C 2O 4)(WO 4)·6H 2O、Na 2Fe(C 2O 4)(S 2O 7)·2H 2O或Na 2Fe(C 2O 4)(HPO 4)·2H 2O中的一种。 Preferably, the chemical formula of the crystalline material is Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Mn( C 2 O 4 )(SO 4 )· 2H 2 O, Na 2 Cu(C 2 O 4 )(SO 4 )· 2H 2 O, Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 )· 2H 2 O, Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )( SO 4 )·2H 2 O, Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 V 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 V 0.2 Fe 0.7 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Co(C 2 O 4 )(SO 4 )·6H 2 O, Na 2 Co(C 2 O 4 )(SeO 4 )·2H 2 O, Na 2 Fe(C 2 O 4 )(SeO 4 )·4H 2 O, Na 2 Fe(C 2 O 4 )(WO 4 )·6H 2 O, Na 2 Fe(C 2 O 4 ) (S 2 O 7 )· 2H 2 O or Na 2 Fe(C 2 O 4 )(HPO 4 )· 2H 2 O.
进一步，在本申请提供的技术方案的基础上，晶体材料的化学式为Na 2Co(C 2O 4)(SO 4)·2H 2O，属于六方晶系，空间群为P-63m，失水温度为180℃，分解温度为300℃，单胞参数为
Figure PCTCN2018122244-appb-000001
Figure PCTCN2018122244-appb-000002
α＝β＝90°，γ＝120°，
Figure PCTCN2018122244-appb-000003
Z＝1； Further, on the basis of the technical solution provided by the present application, the chemical formula of the crystalline material is Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O, which belongs to the hexagonal crystal system, the space group is P-63m, and dehydration The temperature is 180℃, the decomposition temperature is 300℃, and the unit cell parameter is
Figure PCTCN2018122244-appb-000001
Figure PCTCN2018122244-appb-000002
α=β=90°, γ=120°,
Figure PCTCN2018122244-appb-000003
Z=1;
优选地，所述晶体材料的化学式为Na 2Ni(C 2O 4)(SO 4)·2H 2O，属于六方晶系，空间群为P-63m，失水温度为180℃，分解温度为310℃；单胞参数为
Figure PCTCN2018122244-appb-000004
α＝β＝90°，γ＝120°，
Figure PCTCN2018122244-appb-000005
Z＝1。 Preferably, the chemical formula of the crystalline material is Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O, which belongs to the hexagonal crystal system, the space group is P-63m, the water loss temperature is 180°C, and the decomposition temperature is 310℃; unit cell parameter is
Figure PCTCN2018122244-appb-000004
α=β=90°, γ=120°,
Figure PCTCN2018122244-appb-000005
Z=1.
第二方面，本申请提供了一种晶体材料的制备方法，包括以下步骤：将钠源、M源、草酸根源、X源和溶剂混合均匀后进行溶剂热反应，得到晶体材料；In a second aspect, the present application provides a method for preparing a crystalline material, including the following steps: mixing the sodium source, the M source, the oxalate source, the X source, and the solvent, and then performing a solvothermal reaction to obtain a crystalline material;
优选地，钠源、M源、草酸根源和X源的摩尔比为(2-8):1:(1-8):(2-8)；Preferably, the molar ratio of sodium source, M source, oxalate source and X source is (2-8):1:(1-8):(2-8);
优选地，所述钠源包括含钠的氧化物、碱或盐中的至少一种；Preferably, the sodium source includes at least one of oxides, bases or salts containing sodium;
优选地，所述M源包括含M的氧化物、酸、碱、盐或M单质中的至少一种；Preferably, the M source includes at least one of M-containing oxides, acids, bases, salts, or M elements;
优选地，所述草酸根源包括含草酸根的酸或盐中的至少一种；Preferably, the oxalate source includes at least one of oxalate-containing acid or salt;
优选地，所述X源包括含X的酸或盐中的至少一种；Preferably, the X source includes at least one of X-containing acids or salts;
优选地，溶剂为水、醇类、酮类或吡啶类中的至少一种，优选水。Preferably, the solvent is at least one of water, alcohols, ketones or pyridines, preferably water.
进一步，在本申请提供的技术方案的基础上，溶剂热反应的温度为100-300℃，时间为4-100h。Further, on the basis of the technical solution provided by the present application, the temperature of the solvothermal reaction is 100-300° C., and the time is 4-100 h.
优选地，溶剂热反应的温度为180-220℃，时间为48-72h。Preferably, the temperature of the solvothermal reaction is 180-220°C and the time is 48-72h.
第三方面，本申请提供了上述晶体材料，或上述晶体材料的制备方法制备得到的晶体材料在制备正极活性材料中的应用。In a third aspect, the present application provides the above crystalline material, or the application of the crystalline material prepared by the above crystalline material preparation method in the preparation of a positive electrode active material.
第四方面，本申请提供了一种钠离子电池正极材料，包含上述晶体材料，或上述晶体材料的制备方法制备得到的晶体材料。In a fourth aspect, the present application provides a positive electrode material for a sodium ion battery, comprising the above-mentioned crystalline material, or the crystalline material prepared by the above-mentioned crystalline material preparation method.
进一步，在本申请提供的技术方案的基础上，包括正极活性材料、正极导电剂和正极粘结剂；正极活性材料、正极导电剂和正极粘结剂的重量比为(60-90):(5-30):(3-10)；所述正极活性材料为所述的晶体材料；Further, on the basis of the technical solution provided by the present application, the cathode active material, the cathode conductive agent and the cathode binder are included; the weight ratio of the cathode active material, the cathode conductive agent and the cathode binder is (60-90):( 5-30): (3-10); the positive electrode active material is the crystalline material;
进一步，在本申请提供的技术方案的基础上，正极导电剂包括导电炭黑、导电碳球、导电石墨、导电碳纤维、碳纳米管、石墨烯或还原氧化石墨烯中的至少一种；Further, on the basis of the technical solution provided by the present application, the positive electrode conductive agent includes at least one of conductive carbon black, conductive carbon balls, conductive graphite, conductive carbon fiber, carbon nanotubes, graphene, or reduced graphene oxide;
进一步，在本申请提供的技术方案的基础上，正极粘结剂包括聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、 羧甲基纤维素、丁苯橡胶或聚烯烃类中的至少一种。Further, on the basis of the technical solution provided by the present application, the positive electrode binder includes at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber, or polyolefin .
第五方面，本申请提供了一种钠离子电池，包括上述钠离子电池正极材料。According to a fifth aspect, the present application provides a sodium ion battery, including the foregoing positive electrode material for sodium ion batteries.
第六方面，本申请提供了一种设备，包括上述钠离子电池。In a sixth aspect, the present application provides a device, including the above-mentioned sodium ion battery.
与现有技术相比，本申请的有益效果为：Compared with the prior art, the beneficial effects of this application are:
(1)本申请提供的晶体材料的化学式为Na 2M(C 2O 4)X·nH 2O(其中M为至少一种正二价金属离子，X为负二价阴离子基团，0≤n≤12)，该晶体材料属于异质同构，六方晶系，具有微观三维的骨架结构，其中M、C 2O 4和X共同构成骨架，钠离子和水分子不参与骨架的构成。三维的骨架结构中具有丰富的晶格通道供钠离子迁移，提供了用于钠离子的脱嵌和嵌入的有效路径。该晶体材料可以用于钠离子电池的正极活性材料，使包含其的正极活性材料的嵌钠性能大幅度提升，提高正极活性材料的氧化还原电势和结构稳定性。 (1) The chemical formula of the crystalline material provided in this application is Na 2 M(C 2 O 4 )X·nH 2 O (where M is at least one positive divalent metal ion, X is a negative divalent anion group, 0≤n ≤12), the crystal material belongs to heterogeneous, hexagonal crystal system, with a microscopic three-dimensional skeleton structure, in which M, C 2 O 4 and X together constitute the skeleton, and sodium ions and water molecules do not participate in the formation of the skeleton. The three-dimensional skeleton structure has abundant lattice channels for the migration of sodium ions, providing an effective path for the deintercalation and embedding of sodium ions. The crystalline material can be used as a positive electrode active material of a sodium ion battery, which greatly improves the sodium insertion performance of the positive electrode active material containing the same, and improves the redox potential and structural stability of the positive electrode active material.
(2)本申请提供的钠离子电池正极材料，包括上述晶体材料制备的正极活性材料，该钠离子电池正极材料具有嵌钠性能高、氧化还原电势高、循环稳定性好和成本低的优点。(2) The positive electrode material for sodium ion battery provided by the present application includes the positive electrode active material prepared by the above crystalline material. The positive electrode material for sodium ion battery has the advantages of high sodium insertion performance, high redox potential, good cycle stability and low cost.
(3)本申请提供的正极活性材料的制备方法采用溶剂热合成晶体的方法，工艺简单，成本低廉，适于工业化生产。(3) The preparation method of the positive electrode active material provided by this application adopts the method of solvothermal synthesis of crystals. The process is simple, the cost is low, and it is suitable for industrial production.
附图说明BRIEF DESCRIPTION
为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly explain the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings required for the specific embodiments or the description of the prior art. Obviously, the appended The drawings are some embodiments of the present application. For those of ordinary skill in the art, without paying any creative work, other drawings can be obtained based on these drawings.
图1为本申请提供的晶体材料Na 2M(C 2O 4)(SO 4)·nH 2O的结构示意图； FIG. 1 is a schematic structural diagram of the crystalline material Na 2 M(C 2 O 4 )(SO 4 )·nH 2 O provided by this application;
图2为本申请实施例1提供的晶体材料Na 2Co(C 2O 4)(SO 4)·2H 2O的晶体照片图； 2 is a crystal photograph of the crystalline material Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O provided in Example 1 of the present application;
图3为本申请实施例1提供的晶体材料Na 2Co(C 2O 4)(SO 4)·2H 2O的XRD谱图和理论谱图的对比图； 3 is a comparison diagram of the XRD spectrum and the theoretical spectrum of the crystalline material Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O provided in Example 1 of the present application;
图4为本申请实施例1提供的晶体材料Na 2Co(C 2O 4)(SO 4)·2H 2O的热重分析图； 4 is a thermogravimetric analysis diagram of the crystalline material Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O provided in Example 1 of the present application;
图5为本申请实施例21的钠离子半电池的循环稳定性测试图。FIG. 5 is a cycle stability test chart of the sodium ion half-cell of Example 21 of the present application.
具体实施方式detailed description
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。The embodiments of the present application will be described in detail below in conjunction with examples, but those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If no specific conditions are indicated in the examples, the conventional conditions or the conditions recommended by the manufacturer shall be used. The reagents or instruments used do not indicate the manufacturer, are all conventional products that can be obtained through commercial purchase.
本申请中，如果没有特别的说明，本文所提到的所有实施方式以及优选实施方法可以相互组合形成新的技术方案。In this application, unless otherwise specified, all the embodiments and preferred implementation methods mentioned herein can be combined with each other to form a new technical solution.
本申请中，如果没有特别的说明，本文所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。In this application, if there is no special description, all the technical features and preferred features mentioned in this document can be combined with each other to form a new technical solution.
本申请中，如果没有特别的说明，百分数(％)或者份指的是相对于组合物的质量百分数或重量份。In this application, unless otherwise specified, the percentage (%) or part refers to the mass percentage or part by weight relative to the composition.
本申请中，如果没有特别的说明，所涉及的各组分或其优选组分可以相互组合形成新的技术方案。In this application, unless otherwise specified, the involved components or their preferred components can be combined with each other to form a new technical solution.
本申请中，除非有其他说明，数值范围“a～b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“6～22”表示本文中已经全部列出了“6～22”之间的全部实数，“6～22”只是这些数值组合的缩略表示。In this application, unless otherwise stated, the numerical range "a-b" represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "6-22" means that all real numbers between "6-22" have been listed in this article, and "6-22" is just an abbreviated representation of these numerical combinations.
本申请所公开的“范围”以下限和上限的形式，可以分别为一个或多个下限，和一个或多个上限。The forms of the "lower limit" and the upper limit disclosed in the "range" of this application may be one or more lower limits and one or more upper limits, respectively.
本申请中，除非另有说明，各个反应或操作步骤可以顺序进行，也可以不按照顺序进行。优选地，本文中的反应方法是顺序进行的。In this application, unless otherwise stated, each reaction or operation step may be performed sequentially or not. Preferably, the reaction methods herein are performed sequentially.
除非另有说明，本文中所用的专业与科学术语与本领域熟练人员所熟悉的意义相同。此外，任何与 所记载内容相似或均等的方法或材料也可应用于本申请中。Unless otherwise stated, the technical and scientific terms used in this article have the same meaning as those familiar to those skilled in the art. In addition, any method or material similar to or equivalent to that described can also be applied to this application.
根据本申请的第一个方面，提供了一种晶体材料，该晶体材料的化学式为Na 2M(C 2O 4)X·nH 2O，其中M为至少一种正二价金属，X为负二价阴离子基团，且X不为(C 2O 4)，0≤n≤12。 According to the first aspect of the present application, there is provided a crystalline material having a chemical formula of Na 2 M(C 2 O 4 )X·nH 2 O, where M is at least one positive divalent metal and X is negative Divalent anion group, and X is not (C 2 O 4 ), 0≤n≤12.
上述晶体材料属于异质同构，宏观呈六棱柱状或四方柱状，属于六方晶系。该晶体材料具有三维骨架结构，其中M、(C 2O 4)和X共同构成骨架，Na离子和水分子不参与骨架的构成。单位晶胞中包括3分子的平面型[M(C 2O 4)]、3分子的负二价X阴离子基团、6分子的Na离子和若干游离的水分子；其中，负二价X阴离子基团为桥连的阴离子基团。 The above-mentioned crystalline materials are heterogeneous and isomorphic, with a macroscopic hexagonal column shape or a square column shape, and belong to a hexagonal crystal system. The crystalline material has a three-dimensional skeleton structure, in which M, (C 2 O 4 ) and X together constitute the skeleton, and Na ions and water molecules do not participate in the formation of the skeleton. The unit cell includes 3 molecules of planar type [M(C 2 O 4 )], 3 molecules of negative divalent X anion groups, 6 molecules of Na ions, and several free water molecules; of which, negative divalent X anions The group is a bridged anionic group.
具体地，如图1所示，经单晶X射线衍射实验确认，Na 2M(C 2O 4)(SO 4)·nH 2O晶体材料的晶胞微观结构示意图包括：每四个氧原子和两个碳原子形成平面型草酸根基团；每个M金属原子通过氧桥键与草酸根相连，形成平面型[M(C 2O 4)]二维网状平面；硫酸根阴离子基团通过桥键连接相邻的[M(C 2O 4)]二维网状平面，从而形成三维骨架结构；Na离子和水分子分别通过静电作用和氢键稳定在骨架的空隙中。其中，碳氧键长为
Figure PCTCN2018122244-appb-000006
碳碳键长为
Figure PCTCN2018122244-appb-000007
金属-氧键长为
Figure PCTCN2018122244-appb-000008
与钠最近邻的原子有5-7种，键长为
Figure PCTCN2018122244-appb-000009
Specifically, as shown in FIG. 1, it is confirmed by a single crystal X-ray diffraction experiment that the schematic diagram of the unit cell microstructure of the Na 2 M(C 2 O 4 )(SO 4 )·nH 2 O crystal material includes: every four oxygen atoms Forms a planar oxalate group with two carbon atoms; each M metal atom is connected to the oxalate group through an oxygen bridge bond to form a planar [M(C 2 O 4 )] two-dimensional network plane; the sulfate anion group passes Bridge bonds connect adjacent [M(C 2 O 4 )] two-dimensional network planes to form a three-dimensional skeleton structure; Na ions and water molecules are stabilized in the skeleton voids by electrostatic interaction and hydrogen bonding, respectively. Among them, the carbon-oxygen bond length is
Figure PCTCN2018122244-appb-000006
Carbon-carbon bond length is
Figure PCTCN2018122244-appb-000007
The metal-oxygen bond is
Figure PCTCN2018122244-appb-000008
There are 5-7 kinds of atoms nearest to sodium, and the bond length is
Figure PCTCN2018122244-appb-000009
M为至少一种正二价金属，与草酸根结合形成延展的二维网状平面，对M的种类不作限定，可以为一种或一种以上的正二价金属元素，能够满足晶体材料的结构不变即可。M is at least one kind of positive divalent metal, which is combined with oxalate to form an extended two-dimensional network plane. The type of M is not limited. It can be one or more positive divalent metal elements, which can meet the structure of crystalline materials. Just change it.
X为负二价阴离子基团，对X的种类不作限定，能够满足化合价为负二价即可。X阴离子基团可以保证整体构型的电中性原则，有利于金属离子(如Na +)在骨架结构中的快速传导，还能在氧化还原过程中保证结构的稳定性。 X is a negative divalent anion group, and the type of X is not limited, and it is sufficient if the valence of the compound is negative divalent. The X anion group can ensure the electrical neutrality of the overall configuration, which is conducive to the rapid conduction of metal ions (such as Na + ) in the framework structure, and can also ensure the stability of the structure during the redox process.
晶体材料中的结晶水不参与晶体结构的形成，但是结晶水数量过多会影响晶体结构的稳定性。上述晶体材料中结晶水的个数n可以为0、1、2、3、4、5、6、7、8、9、10、11或12。Crystal water in the crystal material does not participate in the formation of the crystal structure, but too much crystal water will affect the stability of the crystal structure. The number n of crystalline water in the crystalline material may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
上述晶体微观的三维的骨架结构中具有丰富的晶格通道供钠离子迁移，提供了用于钠离子的脱嵌和嵌入的有效路径，为钠离子提供更多的活性位点。该晶体材料可以用于钠离子电池的正极活性材料，使正极活性材料的嵌钠性能大幅度提升，提高正极活性材料的氧化还原电势和结构稳定性。The microscopic three-dimensional skeleton structure of the above crystal has abundant lattice channels for sodium ion migration, provides an effective path for deintercalation and insertion of sodium ions, and provides more active sites for sodium ions. The crystalline material can be used as a positive electrode active material of a sodium ion battery, which greatly improves the sodium insertion performance of the positive electrode active material, and improves the redox potential and structural stability of the positive electrode active material.
在一种优选地实施方式中，M为至少一种正二价过渡金属；In a preferred embodiment, M is at least one positive divalent transition metal;
优选M为Ti、V、Cr、Mn、Co、Ni、Cu或Zn中的至少一种，或前述至少一种金属与Fe的组合；Preferably, M is at least one of Ti, V, Cr, Mn, Co, Ni, Cu or Zn, or a combination of at least one of the foregoing metals and Fe;
优选X为(SO 4)、(SeO 4)、(PO 3F)、(HPO4)、(HAsO 4)、(MoO 4)、(WO 4)、(S 2O 7)或(Se 2O 7)阴离子基团中的一种，0≤n≤6。 Preferably X is (SO 4 ), (SeO 4 ), (PO 3 F), (HPO4), (HAsO 4 ), (MoO 4 ), (WO 4 ), (S 2 O 7 ) or (Se 2 O 7 ) One of the anionic groups, 0≤n≤6.
需要说明的是，如果M为两种或两种以上的金属，其各种金属的摩尔数之和与草酸根离子的摩尔数相同，且各种金属元素之间的摩尔比不会影响晶体材料的结构。It should be noted that if M is two or more metals, the sum of the moles of various metals is the same as the moles of oxalate ions, and the molar ratio between the various metal elements will not affect the crystal material Structure.
优选金属M的种类可以使[M(C 2O 4)]二维网状平面的结构更稳定，提供更丰富的钠离子孔道；优选X的种类和进一步优选X为正四面体阴离子基团，可以减少X阴离子基团的空间占比体积，为钠离子孔道提供更多空间，更稳定地连接相邻的[M(C 2O 4)]二维网状平面；优选结晶水的个数可以显著降低结晶水对晶体结构的影响。 Preferably, the type of metal M can make the structure of the [M(C 2 O 4 )] two-dimensional network plane more stable and provide more abundant sodium ion channels; the type of X and further preferably X are regular tetrahedral anionic groups, It can reduce the space proportion volume of X anion group, provide more space for sodium ion channels, and connect the adjacent [M(C 2 O 4 )] two-dimensional network plane more stably; preferably the number of crystal water can be Significantly reduce the effect of crystal water on the crystal structure.
优选晶体材料的化学式可以为但不限于Na 2Co(C 2O 4)(SO 4)·2H 2O、Na 2Ni(C 2O 4)(SO 4)·2H 2O、Na 2Mn(C 2O 4)(SO 4)·2H 2O、Na 2Cu(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.5Mn 0.5(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.75Mn 0.25(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Ti 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9V 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Zn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Cu 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Ti 0.1Fe 0.8Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Ni 0.6Mn 0.2Co 0.2(C 2O 4)(SO 4)·2H 2O、Na 2V 0.1Fe 0.8Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2V 0.2Fe 0.7Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Co(C 2O 4)(SO 4)·6H 2O、Na 2Co(C 2O 4)(SeO 4)·2H 2O、Na 2Fe(C 2O 4)(SeO 4)·4H 2O、Na 2Fe(C 2O 4)(WO 4)·6H 2O、Na 2Fe(C 2O 4)(S 2O 7)·2H 2O 或Na 2Fe(C 2O 4)(HPO 4)·2H 2O中的一种。 The chemical formula of the preferred crystalline material may be, but not limited to, Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Mn( C 2 O 4 )(SO 4 )· 2H 2 O, Na 2 Cu(C 2 O 4 )(SO 4 )· 2H 2 O, Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 )· 2H 2 O, Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )( SO 4 )·2H 2 O, Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 V 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 V 0.2 Fe 0.7 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Co(C 2 O 4 )(SO 4 )·6H 2 O, Na 2 Co(C 2 O 4 )(SeO 4 )·2H 2 O, Na 2 Fe(C 2 O 4 )(SeO 4 )·4H 2 O, Na 2 Fe(C 2 O 4 )(WO 4 )·6H 2 O, Na 2 Fe(C 2 O 4 ) One of (S 2 O 7 )·2H 2 O or Na 2 Fe(C 2 O 4 )(HPO 4 )·2H 2 O.
上述优选的晶体材料，选择四面体型的阴离子基团来作为连接[M(C 2O 4)]二维网状平面的桥梁，可以使晶体材料提供更丰富的孔道供钠离子迁移，为钠离子提供更多的活性位点，提高晶体材料嵌钠性能和结构稳定性。 For the above-mentioned preferred crystalline materials, the tetrahedral anionic group is selected as the bridge connecting the [M(C 2 O 4 )] two-dimensional network plane, which can make the crystalline material provide more abundant channels for the migration of sodium ions. Provide more active sites and improve the sodium intercalation performance and structural stability of crystalline materials.
在一种优选地实施方式中，晶体材料为的化学式为Na 2Co(C 2O 4)(SO 4)·2H 2O，属于六方晶系，空间群为P-63m，失水温度为180℃，分解温度为300℃，单胞参数为
Figure PCTCN2018122244-appb-000010
Figure PCTCN2018122244-appb-000011
α＝β＝90°，γ＝120°，
Figure PCTCN2018122244-appb-000012
Z＝1。 In a preferred embodiment, the crystalline material has the chemical formula Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O, belonging to the hexagonal crystal system, the space group is P-63m, and the water loss temperature is 180 ℃, decomposition temperature is 300℃, unit cell parameter is
Figure PCTCN2018122244-appb-000010
Figure PCTCN2018122244-appb-000011
α=β=90°, γ=120°,
Figure PCTCN2018122244-appb-000012
Z=1.
图2为晶体材料Na 2Co(C 2O 4)(SO 4)·2H 2O的晶体照片图，可以看出该晶体材料微观呈六方柱状。 Fig. 2 is a crystal photograph of the crystalline material Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O. It can be seen that the crystalline material has a hexagonal column shape.
图3为Na 2Co(C 2O 4)(SO 4)·2H 2O晶体的理论和实验的XRD谱图对比，其中，理论谱为由单晶结构推导出的X射线衍射谱。从图3可以看出，实验谱与理论谱的峰吻合的很好，说明实验样品结晶性好，纯度高。此外，衍射峰的相对强度与理论谱有微小差别，这是由于为Na 2Co(C 2O 4)(SO 4)·2H 2O晶体材料的各项异性生长习性造成的。 Fig. 3 is a comparison of the theoretical and experimental XRD spectra of Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O crystal, where the theoretical spectrum is the X-ray diffraction spectrum derived from the single crystal structure. It can be seen from Figure 3 that the peaks of the experimental spectrum and the theoretical spectrum are in good agreement, indicating that the experimental sample has good crystallinity and high purity. In addition, the relative intensity of the diffraction peak is slightly different from the theoretical spectrum, which is caused by the anisotropic growth habit of Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O crystal material.
图4为Na 2Co(C 2O 4)(SO 4)·2H 2O晶体的热重分析图，从图4中可以看出，该物质加热到180摄氏度时，失重达11.03％，对应于失去两个结晶水；继续加热至310摄氏度时，总失重约31％，对应于Na 2Co(C 2O 4)(SO 4)化合物分解成硫酸钠和过渡金属氧化物Co 2O 3。 Fig. 4 is a thermogravimetric analysis diagram of Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O crystal. It can be seen from Fig. 4 that when the substance is heated to 180°C, the weight loss reaches 11.03%, corresponding to Two crystal waters are lost; when heating is continued to 310 degrees Celsius, the total weight loss is about 31%, corresponding to the decomposition of Na 2 Co(C 2 O 4 )(SO 4 ) compounds into sodium sulfate and transition metal oxide Co 2 O 3 .
在一种优选地实施方式中，晶体材料的化学式为Na 2Ni(C 2O 4)(SO 4)·2H 2O，属于六方晶系，空间群为P-63m，失水温度为180℃，分解温度为310℃，单胞参数为
Figure PCTCN2018122244-appb-000013
Figure PCTCN2018122244-appb-000014
α＝β＝90°，γ＝120°，
Figure PCTCN2018122244-appb-000015
Z＝1。 In a preferred embodiment, the chemical formula of the crystalline material is Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O, belonging to the hexagonal crystal system, the space group is P-63m, and the water loss temperature is 180°C , The decomposition temperature is 310℃, and the unit cell parameter is
Figure PCTCN2018122244-appb-000013
Figure PCTCN2018122244-appb-000014
α=β=90°, γ=120°,
Figure PCTCN2018122244-appb-000015
Z=1.
根据本申请的第二个方面，提供了上述晶体材料的制备方法，包括以下步骤：将钠源、M源、草酸根源、X源和溶剂混合均匀后进行溶剂热反应，得到晶体材料；According to the second aspect of the present application, there is provided a method for preparing the above crystalline material, including the following steps: mixing the sodium source, the M source, the oxalate source, the X source and the solvent, and then performing a solvothermal reaction to obtain a crystalline material;
优选溶剂为水，即优选溶剂热反应为水热反应来制备晶体材料，水热反应是指在特指的密闭反应器(高压釜)中，利用水溶液作为反应体系，加热(或自升蒸汽压)，创造一个相对高温和高压的反应环境，使得通常难溶或不溶的物质溶解，并且重结晶而进行无机合成与材料处理的一种有效方法。水热反应后得到的上述晶体材料肉眼可见，宏观为六棱柱状或者四方柱状。Preferably, the solvent is water, that is, the solvothermal reaction is preferably a hydrothermal reaction to prepare crystalline materials. The hydrothermal reaction refers to the use of an aqueous solution as the reaction system in a specific closed reactor (autoclave), heating (or self-rising vapor pressure ), to create a relatively high-temperature and high-pressure reaction environment, so that usually insoluble or insoluble substances are dissolved, and recrystallization is an effective method for inorganic synthesis and material processing. The crystal material obtained after the hydrothermal reaction is visible to the naked eye, and the macroscopic shape is a hexagonal column shape or a square column shape.
需要说明的是，钠源、M源、草酸根源和X源加入溶剂的顺序可以任意调换，优选的顺序为依次加入M源、草酸根源、钠源和X源。It should be noted that the order in which the sodium source, the M source, the oxalate source and the X source are added to the solvent can be arbitrarily changed, and the preferred order is to sequentially add the M source, the oxalate source, the sodium source and the X source.
为了使制备得到的晶体材料的结构更好和缩短制备时间，优选钠源、M源、草酸根源和X源的摩尔比为(2-8):1:(1-8):(2-8)；钠源、M源、草酸根源和X源的摩尔比可以为2:1:8:2、3:1:7:3、4:1:6:4、5:1:5:5、6:1:4:6、7:1:3:7、8:1:2:8或8:1:1:8。In order to make the structure of the prepared crystalline material better and shorten the preparation time, the molar ratio of the sodium source, the M source, the oxalate source and the X source is preferably (2-8):1:(1-8):(2-8 ); The molar ratio of sodium source, M source, oxalate source and X source can be 2:1:8:2, 3:1:7:3, 4:1:6:4, 5:1:5:5, 6:1:4:6, 7:1:3:7, 8:1:2:8 or 8:1:1:8.
钠源包括含钠的氧化物、碱或盐中的至少一种；钠源包括但不限于碳酸钠、乙酸钠、亚硝酸钠、氟硼酸钠、溴化钠、硫酸钠、草酸钠、过硫酸氢钠、氢氧化钠、焦硫酸钠、磷酸二氢钠、磷酸氢二钠、焦亚硫酸钠、焦磷酸钠、硫酸铬钠、酒石酸氢钠、重铬酸钠、邻苯二甲酸氢钠、草酸氢钠、亚硫酸钠、山梨酸钠、氟硅酸钠、磷酸三钠、葡萄糖酸钠或油酸钠中的一种或多种；优选钠源为碳酸钠、氢氧化钠或硫酸钠中的一种或多种；优选硫酸钠。Sources of sodium include at least one of oxides, bases or salts containing sodium; sources of sodium include but are not limited to sodium carbonate, sodium acetate, sodium nitrite, sodium fluoroborate, sodium bromide, sodium sulfate, sodium oxalate, persulfate Sodium hydrogen, sodium hydroxide, sodium pyrosulfate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrosulfite, sodium pyrophosphate, sodium chromium sulfate, sodium hydrogen tartrate, sodium dichromate, sodium hydrogen phthalate, hydrogen oxalate One or more of sodium, sodium sulfite, sodium sorbate, sodium fluorosilicate, trisodium phosphate, sodium gluconate or sodium oleate; preferably the source of sodium is one of sodium carbonate, sodium hydroxide or sodium sulfate or Multiple; sodium sulfate is preferred.
M源包括含M的氧化物、酸、碱、盐或M单质中的至少一种；优选M为Ti、V、Cr、Mn、Fe、Co、Ni、Cu或Zn中的至少一种，或前述至少一种金属与Fe的组合。具体地，M源可以为钛源、钒源、铬源、锰源、铁源、钴源、镍源、铜源或锌源中的一种或多种。The source of M includes at least one of oxides, acids, bases, salts or elements containing M; preferably M is at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, or Combination of at least one of the foregoing metals and Fe. Specifically, the M source may be one or more of a titanium source, a vanadium source, a chromium source, a manganese source, an iron source, a cobalt source, a nickel source, a copper source, or a zinc source.
钛源包括但不限于单质钛、三氧化二钛、二氧化钛、硫酸钛(III)、硫酸钛(IV)、磷酸钛、氟钛酸钠、六氟钛酸、钛酸四丁酯、钛酸四乙酯、钛酸异丙酯、四氯化钛、三氯化钛、二氢化钛、氟钛酸铵、四氟化钛、二氯二茂钛或双(乙酰丙酮基)异丙基钛酸酯及其水合物中的一种或多种；优选钛源为四氟 化钛、硫酸钛(III)或三氯化钛中一种或多种。Titanium sources include but are not limited to elemental titanium, titanium dioxide, titanium dioxide, titanium(III) sulfate, titanium(IV) sulfate, titanium phosphate, sodium fluotitanate, hexafluorotitanic acid, tetrabutyl titanate, tetratitanate Ethyl ester, isopropyl titanate, titanium tetrachloride, titanium trichloride, titanium dihydride, ammonium fluorotitanate, titanium tetrafluoride, titanium dichloride or bis(acetylacetonyl)isopropyl titanate One or more of esters and their hydrates; the preferred source of titanium is one or more of titanium tetrafluoride, titanium (III) sulfate, or titanium trichloride.
钒源包括但不限于单质钒、三氧化二钒、二氧化钒、五氧化二钒、二氟化钒、三氟化钒、四氟化钒、五氟化钒、氟氧化钒、二氯化钒、三氯化钒、四氯化钒、氯氧化钒、二溴化钒、三溴化钒、四溴化钒、偏钒酸铵、正钒酸钠、偏钒酸钠、乙酰丙酮钒、乙酰丙酮氧钒、三异丙氧基氧化钒或三丙醇氧化钒及其水合物中的一种或多种；优选钒源为二氧化钒、五氧化二钒或氟氧化钒中一种或多种。Vanadium sources include but are not limited to elemental vanadium, vanadium trioxide, vanadium dioxide, vanadium pentoxide, vanadium difluoride, vanadium trifluoride, vanadium tetrafluoride, vanadium pentafluoride, vanadium oxyfluoride, dichloride Vanadium, vanadium trichloride, vanadium tetrachloride, vanadium oxychloride, vanadium dibromide, vanadium tribromide, vanadium tetrabromide, ammonium metavanadate, sodium orthovanadate, sodium metavanadate, vanadium acetylacetonate, One or more of vanadium acetylacetonate, triisopropoxy vanadium oxide or tripropanol vanadium oxide and their hydrates; the preferred source of vanadium is one of vanadium dioxide, vanadium pentoxide or vanadium oxyfluoride or Multiple.
铬源包括但不限于单质铬、三氧化铬、二氧化铬、三氧化二铬、氢氧化铬、硫酸铬、硫酸亚铬、亚铬酸锂、重铬酸钾、重铬酸钠、铬钒、三氟化铬、二氯化铬、三氯化铬、溴化铬、溴化亚铬、正磷酸铬、偏磷酸铬、焦磷酸铬、酸式磷酸铬、碱式磷酸铬、磷氯酸铬、硝酸铬、硝酸亚铬、甲酸铬、乙酸镉、乙酸亚铬或草酸铬及其水合物中的一种或多种；优选铬源为氢氧化铬、二氯化铬或三氯化铬中的一种或多种。Chromium sources include but are not limited to elemental chromium, chromium trioxide, chromium dioxide, chromium trioxide, chromium hydroxide, chromium sulfate, chromite sulfate, lithium chromite, potassium dichromate, sodium dichromate, chromium vanadium , Chromium trifluoride, chromium dichloride, chromium trichloride, chromium bromide, chromium bromide, chromium orthophosphate, chromium metaphosphate, chromium pyrophosphate, chromic acid phosphate, basic chromium phosphate, phosphoric acid One or more of chromium, chromium nitrate, chromium nitrate, chromium formate, cadmium acetate, chromium acetate or chromium oxalate and their hydrates; the preferred source of chromium is chromium hydroxide, chromium dichloride or chromium trichloride One or more of them.
锰源包括但不限于单质锰、氧化锰、二氧化锰、四氧化三锰、氟化锰(II)、氟化锰(III)、氯化锰(II)、氯化锰(III)、溴化锰、碳酸锰、硝酸锰、硫酸锰、磷酸锰、磷酸二氢锰、乙酰丙酮锰、甲酸锰、乙酸锰(II)、乙酸锰(III)或草酸锰及其水合物中的一种或多种；优选锰源为乙酸锰、草酸锰或氯化锰中一种或多种。Manganese sources include but are not limited to elemental manganese, manganese oxide, manganese dioxide, trimanganese tetraoxide, manganese (II) fluoride, manganese (III) fluoride, manganese (II) chloride, manganese (III) chloride, bromine One of manganese chloride, manganese carbonate, manganese nitrate, manganese sulfate, manganese phosphate, manganese dihydrogen phosphate, manganese acetylacetonate, manganese formate, manganese (II) acetate, manganese (III) acetate or manganese oxalate and their hydrates or Multiple; preferably, the source of manganese is one or more of manganese acetate, manganese oxalate or manganese chloride.
钴源包括但不限于单质钴、一氧化钴、三氧化二钴、四氧化三钴、氢氧化钴(II)、氢氧化钴(III)、氟化钴(II)、氟化钴(III)、氯化钴(II)、氯化钴(III)、溴化钴、硝酸钴、硫酸钴、碳酸钴、乙酸钴、草酸钴、六氨基氯化钴或乙酰丙酮钴及其水合物中的一种或多种；优选钴源为乙酸钴、草酸钴或氯化钴中的一种或多种。Cobalt sources include but are not limited to elemental cobalt, cobalt monoxide, cobalt trioxide, tricobalt tetroxide, cobalt (II) hydroxide, cobalt (III) hydroxide, cobalt (II) fluoride, cobalt (III) fluoride, chloride One or more of cobalt (II), cobalt chloride (III), cobalt bromide, cobalt nitrate, cobalt sulfate, cobalt carbonate, cobalt acetate, cobalt oxalate, hexaaminocobalt chloride or cobalt acetylacetonate and their hydrates Preferably, the source of cobalt is one or more of cobalt acetate, cobalt oxalate or cobalt chloride.
镍源包括但不限于单质镍、氧化镍、氧化高镍、氢氧化镍、氢氧化高镍、氟化镍、氯化镍、溴化镍、硝酸镍、碳酸镍、硫酸镍、乙酸镍、草酸镍、双(六氟乙基丙酮)合镍、氨基磺酸镍、碱式碳酸镍、乙酰丙酮镍二水合物、三氟甲磺酸镍、苯磺酸镍、乙酰丙酮镍或氟硼酸镍及其水合物中的一种或多种；优选镍源为草酸镍、氯化镍、氟化镍或乙酸镍中的一种或多种。Nickel sources include but are not limited to elemental nickel, nickel oxide, high nickel oxide, nickel hydroxide, high nickel hydroxide, nickel fluoride, nickel chloride, nickel bromide, nickel nitrate, nickel carbonate, nickel sulfate, nickel acetate, oxalic acid Nickel, nickel bis(hexafluoroethylacetone), nickel sulfamate, basic nickel carbonate, nickel acetylacetonate dihydrate, nickel trifluoromethanesulfonate, nickel benzenesulfonate, nickel acetylacetonate or nickel fluoroborate and One or more of its hydrates; preferably, the nickel source is one or more of nickel oxalate, nickel chloride, nickel fluoride, or nickel acetate.
铜源包括但不限于单质铜、氧化亚铜、氧化铜、氢氧化铜、氟化铜、氯化铜、溴化铜、碳酸铜、碱式碳酸铜、硝酸铜、硫酸铜、乙酸铜、草酸铜、酒石酸铜、柠檬酸铜、氟硼酸铜、乙酰丙酮铜或葡萄糖酸铜及其水合物中的一种或多种；优选铜源为醋酸铜、硫酸铜或氯化铜中的一种或多种。Copper sources include but are not limited to elemental copper, cuprous oxide, copper oxide, copper hydroxide, copper fluoride, copper chloride, copper bromide, copper carbonate, basic copper carbonate, copper nitrate, copper sulfate, copper acetate, oxalic acid One or more of copper, copper tartrate, copper citrate, copper fluoroborate, copper acetylacetonate or copper gluconate and their hydrates; the preferred copper source is one of copper acetate, copper sulfate or copper chloride or Multiple.
锌源包括但不限于单质锌、氧化锌、氢氧化锌、氟化锌、氯化锌、溴化锌、碘化锌、硫酸锌、硝酸锌、碳酸锌、乙酸锌、草酸锌、柠檬酸锌、氟硼酸锌、酒石酸锌、硼酸锌、偏硼酸锌、乙酰丙酮锌或葡萄糖酸锌及其水合物中的一种或多种；优选锌源为硫酸锌或氯化锌中的一种或两种。Zinc sources include but are not limited to elemental zinc, zinc oxide, zinc hydroxide, zinc fluoride, zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, zinc carbonate, zinc acetate, zinc oxalate, zinc citrate , Zinc fluoroborate, zinc tartrate, zinc borate, zinc metaborate, zinc acetylacetonate or zinc gluconate and one or more of their hydrates; the preferred zinc source is one or both of zinc sulfate or zinc chloride Species.
铁源包括但不限于单质铁、三氧化二铁、四氧化三铁、氢氧化亚铁、氢氧化铁、氟化亚铁、氟化铁、氯化亚铁、氯化铁、溴化亚铁、溴化铁、甲酸铁、乙酸亚铁、硝酸亚铁、硫酸亚铁、硝酸铁、硫酸铁、乙酰丙酮铁、草酸亚铁、草酸铁及其水合物中的一种或者多种；优选铁源为草酸亚铁、氯化亚铁及其水合物中的一种或多种。Iron sources include but are not limited to elemental iron, ferric oxide, ferric oxide, ferrous hydroxide, ferric hydroxide, ferrous fluoride, ferric fluoride, ferrous chloride, ferric chloride, ferrous bromide , Iron bromide, iron formate, ferrous acetate, ferrous nitrate, ferrous sulfate, ferric nitrate, ferric sulfate, ferric acetylacetonate, one or more of ferrous oxalate, ferric oxalate and their hydrates; preferably iron The source is one or more of ferrous oxalate, ferrous chloride and their hydrates.
草酸根源包括含草酸根的酸或盐中的至少一种；草酸根源包括但不限于草酸、草酸钠、草酸氢钠、草酸铵或草酸二乙酯及其水合物中的一种或多种；优选草酸及其水合物。The oxalate source includes at least one of oxalate-containing acids or salts; oxalate source includes but is not limited to one or more of oxalic acid, sodium oxalate, sodium hydrogen oxalate, ammonium oxalate, or diethyl oxalate, and hydrates thereof; Oxalic acid and its hydrates are preferred.
X源为负二价阴离子基团的来源，可以为但不限于含X的酸或盐中的至少一种。优选X为(SO 4)、(SeO 4)、(PO 3F)、(HPO4)、(HAsO 4)、(MoO 4)、(WO 4)、(S 2O 7)或(Se 2O 7)阴离子基团中的一种。具体地，X源可以为硫酸根源、硒酸根源、氟化磷酸根源、一氢磷酸根源、一氢砷酸根源、钼酸根源、钨酸根源、焦硫酸根源或焦硒酸根源中的一种。 The source of X is a source of a negative dianion group, and may be, but not limited to, at least one of X-containing acids or salts. Preferably X is (SO 4 ), (SeO 4 ), (PO 3 F), (HPO4), (HAsO 4 ), (MoO 4 ), (WO 4 ), (S 2 O 7 ) or (Se 2 O 7 ) One of the anionic groups. Specifically, the X source may be one of a sulfate source, a selenate source, a fluoride phosphate source, a monohydrogen phosphate source, a monohydroarsenate source, a molybdate source, a tungstate source, a pyrosulfate source, or a pyroselenate source. .
硫酸根源包括但不限于硫酸酐、硫酸溶液、碱金属硫酸盐、碱土金属硫酸盐、硫酸铵、硫酸氢铵或所需过渡金属硫酸盐中的一种或多种；优选硫酸和硫酸钠中的一种或两种。Sources of sulfate include, but are not limited to, one or more of sulfuric anhydride, sulfuric acid solution, alkali metal sulfate, alkaline earth metal sulfate, ammonium sulfate, ammonium bisulfate, or desired transition metal sulfate; preferably sulfuric acid and sodium sulfate One or two.
硒酸根源包括但不限于硒酸酐、硒酸、碱金属硒酸盐、碱土金属硒酸盐、硒酸铵、硒酸氢铵或所需过渡金属硒酸盐中的一种或多种；优选硒酸和硒酸钠中的一种或两种。Sources of selenate include, but are not limited to, one or more of selenic anhydride, selenic acid, alkali metal selenate, alkaline earth metal selenate, ammonium selenate, ammonium hydrogen selenate, or desired transition metal selenate; preferably One or both of selenic acid and sodium selenate.
氟化磷酸根源包括但不限于氟化磷酸、氟化磷酸锂、氟化磷酸钠、氟化磷酸钾、氟化磷酸铵或氟化磷酸铷中的一种或多种；优选氟化磷酸和氟化磷酸钠中的一种或两种。Sources of fluorinated phosphate include, but are not limited to, one or more of fluorinated phosphoric acid, lithium fluorinated phosphate, sodium fluorinated phosphate, potassium fluorinated phosphate, ammonium fluorinated phosphate, or rubidium fluorinated phosphate; preferably fluorinated phosphoric acid and fluorine One or two of sodium phosphate.
一氢磷酸根源包括但不限于磷酸酸酐、磷酸、碱金属磷酸一氢盐、碱土金属磷酸一氢盐或所需过渡金属磷酸一氢盐中的一种或多种；优选磷酸一氢钠和过渡金属磷酸盐中的一种或两种。Sources of monohydrogen phosphate include, but are not limited to, one or more of phosphoric anhydride, phosphoric acid, alkali metal monohydrogen phosphate, alkaline earth metal monohydrogen phosphate, or the desired transition metal monohydrogen phosphate; preferably sodium monohydrogen phosphate and transition One or two of the metal phosphates.
一氢砷酸根源包括但不限于砷酸酐、砷酸溶液、碱金属砷酸盐、碱土金属砷酸盐、砷酸铵、砷酸氢铵或所需过渡金属砷酸盐中的一种或多种；优选砷酸和砷酸钠中的一种或两种。Sources of monohydroarsenic acid include, but are not limited to, one or more of arsenic anhydride, arsenic acid solution, alkali metal arsenate, alkaline earth metal arsenate, ammonium arsenate, ammonium hydrogen arsenate, or desired transition metal arsenate It is preferably one or both of arsenic acid and sodium arsenate.
钼酸根源包括但不限于三氧化二钼、三氧化钼、钼酸溶液、碱金属钼酸盐、碱土金属钼酸盐、钼酸铵、钼酸氢铵或所需过渡金属钼酸盐中的一种或多种；优选钼酸和钼酸钠中的一种或两种。Molybdate sources include, but are not limited to, molybdenum trioxide, molybdenum trioxide, molybdic acid solution, alkali metal molybdate, alkaline earth metal molybdate, ammonium molybdate, ammonium hydrogen molybdate, or the desired transition metal molybdate. One or more; preferably one or two of molybdic acid and sodium molybdate.
钨酸根源包括但不限于钨酸酐、钨酸溶液、碱金属钨酸盐、碱土金属钨酸盐、钨酸铵、钨酸氢铵或所需过渡金属钨酸盐中的一种或多种；优选钨酸和钨酸钠中的一种或两种。Tungstic acid sources include, but are not limited to, one or more of tungstic anhydride, tungstic acid solution, alkali metal tungstate, alkaline earth metal tungstate, ammonium tungstate, ammonium hydrogen tungstate, or desired transition metal tungstate; One or both of tungstic acid and sodium tungstate are preferred.
焦硫酸根源包括但不限于焦硫酸酐、焦硫酸溶液、碱金属焦硫酸盐、碱土金属焦硫酸盐、焦硫酸铵、焦硫酸氢铵或所需过渡金属焦硫酸盐中的一种或多种；优选焦硫酸和焦硫酸钠中的一种或两种。Sources of pyrosulfate include, but are not limited to, one or more of pyrosulfuric anhydride, pyrosulfuric acid solution, alkali metal pyrosulfate, alkaline earth metal pyrosulfate, ammonium pyrosulfate, ammonium pyrosulfate, or desired transition metal pyrosulfate ; Preferably one or both of pyrosulfuric acid and sodium pyrosulfate.
焦硒酸根源包括但不限于焦硒酸酐、焦硒酸溶液、碱金属焦硒酸盐、碱土金属焦硒酸盐、焦硒酸铵、焦硒酸氢铵或所需过渡金属焦硒酸盐中的一种或多种；优选焦硒酸和焦硒酸钠中的一种或两种。Pyroselenate sources include, but are not limited to, pyroselenic acid anhydride, pyroselenic acid solution, alkali metal pyroselenate, alkaline earth metal pyroselenate, ammonium pyroselenate, ammonium pyroselenate, or desired transition metal pyroselenate One or more of them; preferably one or both of pyroselenic acid and sodium pyroselenate.
需要说明的是，上述提供钠源、M源、草酸根源和X阴离子源的化合物的水合物也可以作为水热合成的原料来源，水合物不会影响制备得到的晶体结构。It should be noted that the hydrates of the compounds that provide the sodium source, the M source, the oxalate source, and the X anion source can also be used as raw material sources for hydrothermal synthesis, and the hydrates will not affect the prepared crystal structure.
上述溶剂为水、醇类、酮类或吡啶类中的至少一种；优选溶剂包括但不限于水、甲醇、乙醇、丙酮、乙二醇或吡啶中的一种或多种，优选水。The above solvent is at least one of water, alcohols, ketones or pyridines; preferred solvents include but are not limited to one or more of water, methanol, ethanol, acetone, ethylene glycol or pyridine, preferably water.
在一种优选地实施方式中，溶剂热反应的温度为100-300℃，时间为4-100h；优选溶剂热反应的温度为180-220℃，时间为48-72h。In a preferred embodiment, the temperature of the solvothermal reaction is 100-300°C and the time is 4-100h; the temperature of the solvothermal reaction is 180-220°C and the time is 48-72h.
溶剂热反应的温度典型但非限制性的例如为100℃、130℃、150℃、180℃、200℃、230℃、270℃或300℃；溶剂热反应的时间典型但非限制性的例如为4h、10h、20h、30h、40h、50h、60h、70h、80h、90h或100h。The temperature of the solvothermal reaction is typically, but not limited to, for example, 100°C, 130°C, 150°C, 180°C, 200°C, 230°C, 270°C, or 300°C; the time of the solvothermal reaction is typical, but not limited to, for example: 4h, 10h, 20h, 30h, 40h, 50h, 60h, 70h, 80h, 90h or 100h.
一种示例性的晶体材料的制备方法，包括以下步骤：An exemplary method for preparing a crystalline material includes the following steps:
(a)按照一定比例称量钠源、M源、草酸根源和X阴离子源，将称量的原料加入装有溶剂的反应器中，混合均匀后得到混合溶液；(a) Weigh the sodium source, the M source, the oxalate source and the X anion source according to a certain ratio, add the weighed raw materials to the reactor equipped with a solvent, mix them evenly to obtain a mixed solution;
(b)将混合溶液在温度100-300℃加热4-100h，得到晶体材料初产物；(b) Heating the mixed solution at a temperature of 100-300°C for 4-100h to obtain the crystalline material initial product;
(c)将晶体材料初产物经过洗涤和干燥后得到晶体材料。(c) The crystalline material is obtained after washing and drying the initial product of the crystalline material.
应当说明的是，步骤(a)中的原料加料顺序没有特殊限制，只要混合后能得到均匀的混合溶液即可。It should be noted that the order of raw material addition in step (a) is not particularly limited, as long as a uniform mixed solution can be obtained after mixing.
该示例性的晶体材料的制备方法限定了制备过程的工艺参数，清楚地显示了各工艺步骤的顺序关系，按照该示例性的制备方法，可以缩短制备工艺时间，得到纯度更好的晶体材料。The exemplary method for preparing a crystalline material defines the process parameters of the manufacturing process, and clearly shows the sequence relationship of each process step. According to this exemplary method, the preparation process time can be shortened, and a crystal material with better purity can be obtained.
根据本申请的第三个方面，提供了上述晶体材料在制备正极活性材料中的用途。According to the third aspect of the present application, the use of the above-mentioned crystalline material in preparing a positive electrode active material is provided.
鉴于上述晶体材料具有微观的三维骨架结构，三维的骨架结构中具有丰富的晶格通道供钠离子迁移，提供有效的钠离子的脱嵌和嵌入的扩散路径，为钠离子提供更多的活性位点，所以可以将该晶体材料用于钠离子电池的正极活性材料。In view of the above-mentioned crystal material has a microscopic three-dimensional skeleton structure, the three-dimensional skeleton structure has abundant lattice channels for the migration of sodium ions, provides an effective sodium ion deintercalation and embedded diffusion path, and provides more active sites for sodium ions Point, so this crystalline material can be used as a positive electrode active material for sodium ion batteries.
需要说明的是，由于上述制备方法得到的晶体材料的颗粒较大，粒度约为4-5mm且肉眼可见，所以用于钠离子电池的正极活性材料需要对其进行研磨后使用，优选研磨后的粒度为100-2000nm。对晶 体材料进行研磨且优选研磨后的粒度可以增加其与电解液接触面积，提供更多的钠离子活性位点。It should be noted that, because the crystal material obtained by the above preparation method has large particles, the particle size is about 4-5 mm and is visible to the naked eye, the positive electrode active material used in the sodium ion battery needs to be used after grinding, preferably after grinding The particle size is 100-2000nm. Grinding the crystalline material and preferably the particle size after grinding can increase its contact area with the electrolyte and provide more active sites for sodium ions.
根据本申请的第四个方面，提供了一种钠离子电池正极材料，括正极活性材料、正极导电剂和正极粘结剂；正极活性材料、正极导电剂和正极粘结剂的重量比为(60-90):(5-30):(3-10)；正极活性材料为上述的晶体材料。According to the fourth aspect of the present application, there is provided a sodium ion battery cathode material, including a cathode active material, a cathode conductive agent and a cathode binder; the weight ratio of the cathode active material, the cathode conductive agent and the cathode binder is ( 60-90): (5-30): (3-10); the positive electrode active material is the above-mentioned crystalline material.
正极活性材料、正极导电剂和正极粘结剂的重量比典型但非限制性的例如为60:30:10、65:25:10、70:23:7、75:17:8、80:10:10、85:6:9或90:5:10。The weight ratio of the positive electrode active material, the positive electrode conductive agent and the positive electrode binder are typical but non-limiting examples are, for example, 60:30:10, 65:25:10, 70:23:7, 75:17:8, 80:10 :10, 85:6:9 or 90:5:10.
导电剂是为了保证电极具有良好的导电性能，制作正极电极时通常加入一定量的导电物质，在活性物质之间、活性物质与集流体之间起到收集微电流的作用，以减小电极的接触电阻加速电子的移动速率，同时也能有效地提高钠离子在电极材料中的迁移速率，从而提高电极的充放电效率。正极导电剂可以为但不限于导电炭黑、导电碳球、导电石墨、导电碳纤维、碳纳米管、石墨烯或还原氧化石墨烯中的至少一种。The conductive agent is to ensure that the electrode has good conductivity. When making a positive electrode, a certain amount of conductive material is usually added to collect micro-current between the active material and the active material and the current collector to reduce the electrode. The contact resistance accelerates the moving rate of electrons, and can also effectively increase the migration rate of sodium ions in the electrode material, thereby improving the charge and discharge efficiency of the electrode. The positive electrode conductive agent may be, but not limited to, at least one of conductive carbon black, conductive carbon spheres, conductive graphite, conductive carbon fiber, carbon nanotubes, graphene, or reduced graphene oxide.
粘结剂可以保证电池在使用过程中活性物质颗粒间以及活性颗粒与集流体间具有一定的粘结强度，且有利于SEI膜形成，提高了电极的循环性能和使用寿命。正极粘结剂可以为但不限于聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、丁苯橡胶(SBR)或聚烯烃类中的至少一种。The binder can ensure that the battery has a certain bonding strength between the active material particles and between the active particles and the current collector during the use of the battery, and it is conducive to the formation of the SEI film and improves the cycle performance and service life of the electrode. The positive electrode binder may be, but not limited to, at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber (SBR), or polyolefins.
优选正极活性材料、正极导电剂和正极粘结剂的重量比以及所使用的正极导电剂和正极粘结剂的种类，有利于正极活性物质很好地附着在集流体上，提高正极的充放电效率，使制备的钠离子电池正极材料的电化学性能更好。Preferably, the weight ratio of the positive electrode active material, the positive electrode conductive agent and the positive electrode binder, and the types of the positive electrode conductive agent and the positive electrode binder used are good for the positive electrode active material to adhere well to the current collector and improve the charge and discharge of the positive electrode The efficiency improves the electrochemical performance of the prepared cathode material of sodium ion batteries.
采用上述晶体材料Na 2M(C 2O 4)X·nH 2O(其中M为正二价金属，X负二价阴离子基团，且X不为(C 2O 4)，0≤n≤12)作为钠离子电池正极材料的正极活性材料，使该钠离子电池正极材料具有与上述晶体材料和上述正极活性材料相同的优点，该钠离子电池正极材料具有嵌钠性能高、氧化还原电势高、循环稳定性好和成本低的优点。 Using the above crystalline material Na 2 M(C 2 O 4 )X·nH 2 O (where M is a positive divalent metal, X is a negative divalent anion group, and X is not (C 2 O 4 ), 0≤n≤12 ) As the positive electrode active material of the sodium ion battery positive electrode material, the sodium ion battery positive electrode material has the same advantages as the above crystalline material and the above positive electrode active material, the sodium ion battery positive electrode material has high sodium insertion performance, high redox potential, The advantages of good cycle stability and low cost.
根据本申请的第五个方面，提供了一种钠离子电池，包括上述钠离子电池正极材料。According to a fifth aspect of the present application, there is provided a sodium ion battery, including the foregoing positive electrode material for sodium ion batteries.
钠离子电池的形态可以为但不限于扣式电池、平板电池或圆柱形电池。The shape of the sodium ion battery may be, but not limited to, a button battery, a flat battery, or a cylindrical battery.
钠离子电池的工作原理与锂离子电池相似，为了避免金属钠在负极析出，钠离子电池负极设计比容量应高于正极，使得正极材料决定了钠离子电池容量。采用本申请提供的正极活性材料或钠离子电池正极材料作为正极使用，使该钠离子电池具有电池容量大，循环稳定性好和成本低的优点。The working principle of sodium ion batteries is similar to that of lithium ion batteries. In order to avoid the precipitation of metallic sodium at the negative electrode, the specific capacity of the negative electrode of the sodium ion battery should be higher than that of the positive electrode, so that the positive electrode material determines the capacity of the sodium ion battery. The positive electrode active material provided in the present application or the positive electrode material of a sodium ion battery is used as a positive electrode, so that the sodium ion battery has the advantages of large battery capacity, good cycle stability and low cost.
需要说明的是，除上述的钠离子正极材料之外，钠离子电池还包括负极材料、负极集流体、正极集流体、电解液和隔膜。It should be noted that, in addition to the above-mentioned sodium ion positive electrode material, the sodium ion battery further includes a negative electrode material, a negative electrode current collector, a positive electrode current collector, an electrolyte, and a separator.
在一种优选地实施方式中，负极材料包括负极活性材料、负极导电剂和负极粘结剂，负极活性材料、负极导电剂和负极粘结剂的重量比为(60-90):(5-30):(3-10)；In a preferred embodiment, the negative electrode material includes a negative electrode active material, a negative electrode conductive agent and a negative electrode binder, and the weight ratio of the negative electrode active material, negative electrode conductive agent and negative electrode binder is (60-90):(5- 30): (3-10);
优选负极活性材料可以为但不限于碳材料、金属、合金、硫化物、氮化物、氧化物或碳化物中的至少一种。Preferably, the negative electrode active material may be, but not limited to, at least one of carbon materials, metals, alloys, sulfides, nitrides, oxides, or carbides.
优选负极导电剂可以为但不限于导电炭黑、导电碳球、导电石墨、导电碳纤维、碳纳米管、石墨烯或还原氧化石墨烯中的至少一种；优选负极粘结剂可以为但不限于聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、丁苯橡胶或聚烯烃类中的至少一种。Preferably, the negative electrode conductive agent may be, but not limited to, at least one of conductive carbon black, conductive carbon balls, conductive graphite, conductive carbon fiber, carbon nanotubes, graphene, or reduced graphene oxide; preferably, the negative electrode binder may be, but not limited to At least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber, or polyolefin.
优选负极集流体和正极集流体的材料均独立地包括铝、铜、铁、锡、锌、镍、钛、锰、铅、锑、镉、金、铋或锗中的一种或上述金属的合金或上述金属的复合材料；Preferably, the materials of the negative electrode current collector and the positive electrode current collector independently include one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, or germanium, or an alloy of the above metals Or composite materials of the above metals;
优选负极导电剂和负极粘结剂及其添加量，有利于负极活性物质能够很好地附着在负极集流体上，提高负极的充放电效率。The negative electrode conductive agent, the negative electrode binder and the added amount thereof are preferred, which is favorable for the negative electrode active material to adhere well to the negative electrode current collector and improve the charge and discharge efficiency of the negative electrode.
在一种优选地实施方式中，电解液包括电解质和电解液溶剂；电解质为钠盐。In a preferred embodiment, the electrolyte includes an electrolyte and an electrolyte solvent; the electrolyte is a sodium salt.
优选钠盐在电解液中的摩尔浓度为0.1-10mol/L，钠盐的摩尔浓度典型但非限制性的例如为0.1mol/L、1mol/L、2mol/L、3mol/L、4mol/L、5mol/L、6mol/L、7mol/L、8mol/L、9mol/L或10mol/L。Preferably, the molar concentration of sodium salt in the electrolyte is 0.1-10mol/L, and the molar concentration of sodium salt is typically, but not limited to, for example, 0.1mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L , 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L.
需要说明的是，作为电解质的钠盐没有特别限制，只要可以离解成阳离子和阴离子即可。钠盐可以为但不限于高氯酸钠、六氟磷酸钠、氯化钠、氟化钠、硫酸钠、碳酸钠、磷酸钠、硝酸钠、二氟草酸硼酸钠、焦磷酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、柠檬酸三钠、偏硼酸钠、硼酸钠、钼酸钠、钨酸钠、溴化钠、亚硝酸钠、碘酸钠、碘化钠、硅酸钠、木质素磺酸钠、草酸钠、铝酸钠、甲基磺酸钠、醋酸钠、重铬酸钠、六氟砷酸钠、四氟硼酸钠、三氟甲烷磺酰亚胺钠、NaCF 3SO 3或NaN(SO 2CF 3) 2中的一种或几种，优选高氯酸钠。 It should be noted that the sodium salt as the electrolyte is not particularly limited as long as it can be dissociated into cations and anions. The sodium salt may be, but not limited to, sodium perchlorate, sodium hexafluorophosphate, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate borate, sodium pyrophosphate, dodecane Sodium benzenesulfonate, sodium dodecyl sulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodide, sodium iodide, silicon Sodium, sodium lignosulfonate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium trifluoromethanesulfonimide, One or more of NaCF 3 SO 3 or NaN(SO 2 CF 3 ) 2 , preferably sodium perchlorate.
需要说明的是，电解液溶剂没有特别限制，只要电解液溶剂可以使电解质离解成阳离子和阴离子，且阳离子和阴离子可以自由迁移即可。优选溶剂包括酯类、砜类、醚类或腈类中的一种或几种；具体地，溶剂可以为但不限于碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、甲酸甲酯(MF)、乙酸甲酯(MA)、N,N-二甲基乙酰胺(DMA)、氟代碳酸乙烯酯(FEC)、丙酸甲酯(MP)、丙酸乙酯(EP)、乙酸乙酯(EA)、γ-丁内酯(GBL)、四氢呋喃(THF)、2-甲基四氢呋喃(2MeTHF)、1,3-二氧环戊烷(DOL)、4-甲基-1,3-二氧环戊烷(4MeDOL)、二甲氧甲烷(DMM)、1,2-二甲氧丙烷(DMP)、三乙二醇二甲醚(DG)、二甲基砜(MSM)、二甲醚(DME)、亚硫酸乙烯酯(ES)、亚硫酸丙烯脂(PS)、亚硫酸二甲脂(DMS)、亚硫酸二乙脂(DES)、冠醚(12-冠-4)、1-乙基-3-甲基咪唑-六氟磷酸盐、1-乙基-3-甲基咪唑-四氟硼酸盐、1-乙基-3-甲基咪唑-双三氟甲基磺酰亚胺盐、1-丙基-3-甲基咪唑-六氟磷酸盐、1-丙基-3-甲基咪唑-四氟硼酸盐、1-丙基-3-甲基咪唑-双三氟甲基磺酰亚胺盐、1-丁基-1-甲基咪唑-六氟磷酸盐、1-丁基-1-甲基咪唑-四氟硼酸盐、1-丁基-1-甲基咪唑-双三氟甲基磺酰亚胺盐、N-丁基-N-甲基吡咯烷-双三氟甲基磺酰亚胺盐、1-丁基-1-甲基吡咯烷-双三氟甲基磺酰亚胺盐、N-甲基-N-丙基吡咯烷-双三氟甲基磺酰亚胺盐、N-甲,丙基哌啶-双三氟甲基磺酰亚胺盐或N-甲,丁基哌啶-双三氟甲基磺酰亚胺盐中的一种或多种。It should be noted that the electrolyte solvent is not particularly limited, as long as the electrolyte solvent can dissociate the electrolyte into cations and anions, and the cations and anions can freely migrate. Preferred solvents include one or more of esters, sulfones, ethers or nitriles; specifically, the solvent may be, but not limited to, propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate ( DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate Ester (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), γ-butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF) , 1,3-dioxolane (DOL), 4-methyl-1,3-dioxolane (4MeDOL), dimethoxymethane (DMM), 1,2-dimethoxypropane (DMP ), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl ether (DME), vinyl sulfite (ES), propylene sulfite (PS), dimethyl sulfite ( DMS), diethyl sulfite (DES), crown ether (12-crown-4), 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetra Fluoborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonimide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3- Methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonimide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1- Butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonimide salt, N-butyl-N-methylpyrrolidine-bis Trifluoromethylsulfonimide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonimide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethyl One of sulfonimide salt, N-methyl, propylpiperidine-bis-trifluoromethylsulfonimide salt or N-methyl, butylpiperidine-bis-trifluoromethylsulfonimide salt or Multiple.
优选电解液溶剂和钠盐可以使钠盐更好地溶解，使钠离子自由迁移更方便。电解液中钠盐浓度过低，离子传输性能差，导电率低；钠盐浓度过高，离子过多，电解液的粘度和离子缔合的程度也会随钠盐浓度增加而增大，这又会降低电导率，优选钠盐的摩尔浓度可以避免钠盐浓度过低或过高造成的影响。It is preferable that the electrolyte solvent and the sodium salt can dissolve the sodium salt better and make the sodium ion freely move more conveniently. The sodium salt concentration in the electrolyte is too low, the ion transmission performance is poor, and the conductivity is low; the sodium salt concentration is too high, too many ions, the viscosity of the electrolyte and the degree of ion association will also increase with the increase of the sodium salt concentration, which It will also reduce the electrical conductivity. The molar concentration of sodium salt is preferred to avoid the effects caused by too low or too high sodium salt concentration.
在一种优选地实施方式中，电解液中还包括添加剂；添加剂在电解液中的质量分数为0.1-20％。In a preferred embodiment, the electrolyte further includes additives; the mass fraction of the additives in the electrolyte is 0.1-20%.
添加剂的质量分数典型但非限制性的例如为0.1％、1％、5％、8％、10％、12％、14％、16％、18％或20％。Typical but non-limiting examples of the mass fraction of additives are 0.1%, 1%, 5%, 8%, 10%, 12%, 14%, 16%, 18% or 20%.
在电解液中增加的添加剂可以在负极集流体表面可以形成稳定的固体电解质膜，提高电池的使用寿命。添加剂包括但不限于酯类、砜类、醚类、腈类或烯烃类中的一种或多种。具体地，添加剂可以为但不限于氟代碳酸乙烯酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、1,3-丙磺酸内酯、1,4-丁磺酸内酯、硫酸乙烯酯、硫酸丙烯酯、硫酸亚乙酯、亚硫酸乙烯酯、亚硫酸丙烯酯、二甲基亚硫酸酯、二乙基亚硫酸酯、亚硫酸亚乙酯、氯代甲酸甲脂、二甲基亚砜、苯甲醚、乙酰胺、二氮杂苯、间二氮杂苯、冠醚12-冠-4、冠醚18-冠-6、4-氟苯甲醚、氟代链状醚、二氟代甲基碳酸乙烯酯、三氟代甲基碳酸乙烯酯、氯代碳酸乙烯酯、溴代碳酸乙烯酯、三氟乙基膦酸、溴代丁内酯、氟代乙酸基乙烷、磷酸酯、亚磷酸酯、磷腈、乙醇胺、碳化二甲胺、环丁基砜、1,3-二氧环戊烷、乙腈、长链烯烃、三氧化二铝、氧化镁、氧化钡、碳酸钠、碳酸钙、二氧化碳、二氧化硫或碳酸锂中的一种或几种。Additives added in the electrolyte can form a stable solid electrolyte membrane on the surface of the negative electrode current collector, increasing the service life of the battery. Additives include but are not limited to one or more of esters, sulfones, ethers, nitriles or olefins. Specifically, the additives may be, but not limited to, fluoroethylene carbonate, vinylene carbonate, ethylene ethylene carbonate, 1,3-propane sultone, 1,4-butane sultone, vinyl sulfate, Propylene sulfate, ethylene sulfate, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide , Anisole, acetamide, diazabenzene, m-diazepine, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluoroanisole, fluorochain ether, difluoro Ethylene methyl carbonate, trifluoromethyl ethylene carbonate, chloroethylene carbonate, brominated ethylene carbonate, trifluoroethylphosphonic acid, bromobutyrolactone, fluoroacetoxyethane, phosphate , Phosphite, phosphazene, ethanolamine, carbodimethylamine, cyclobutyl sulfone, 1,3-dioxolane, acetonitrile, long-chain olefins, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, One or more of calcium carbonate, carbon dioxide, sulfur dioxide, or lithium carbonate.
优选隔膜包括但不限于绝缘多孔聚合物薄膜或无机多孔薄膜，具体地，隔膜包括但不限于多孔聚丙烯薄膜、多孔聚乙烯薄膜、玻璃纤维纸或多孔陶瓷隔膜中的一种或多种。优选隔膜的材质可以减少电池内阻和提高电池的循环使用寿命。Preferred separators include but are not limited to insulating porous polymer films or inorganic porous films. Specifically, the separators include but are not limited to one or more of porous polypropylene films, porous polyethylene films, fiberglass paper or porous ceramic separators. Preferably, the material of the separator can reduce the internal resistance of the battery and increase the cycle life of the battery.
一种示例性的钠离子电池的制备方法，包括以下步骤：An exemplary method for preparing a sodium ion battery includes the following steps:
(a)制备钠离子电池正极：将正极活性材料、正极导电剂和正极粘结剂及溶剂混合制成正极材料浆料，经涂覆于正极集流体后干燥、辊压和裁切制成钠离子电池正极；(a) Preparation of positive electrode for sodium ion battery: positive electrode active material, positive electrode conductive agent, positive electrode binder and solvent are mixed to make positive electrode material slurry, which is coated on positive electrode current collector, dried, rolled and cut to make sodium ion Battery positive
(b)制备钠离子电池负极：将负极活性材料、负极导电剂和负极粘结剂及溶剂混合制成负极材料浆料，经涂覆于负极集流体后干燥、辊压和裁切制成钠离子电池负极；(b) Preparation of a negative electrode for a sodium ion battery: a negative electrode active material, a negative electrode conductive agent, a negative electrode binder and a solvent are mixed to make a negative electrode material slurry, which is coated on a negative electrode current collector, dried, rolled and cut to make sodium ions Battery negative;
(c)配制电解液：将钠盐溶于溶剂中，加入添加剂，混合得到电解液；(c) Preparation of electrolyte: dissolve the sodium salt in the solvent, add additives and mix to obtain the electrolyte;
(d)制备隔膜：将隔膜裁切，清洗；(d) Preparation of the diaphragm: cutting and cleaning the diaphragm;
(e)将钠离子电池正极、钠离子电池负极和隔膜进行组装，并注入电解液，得到钠离子电池。(e) Assemble the positive electrode of the sodium ion battery, the negative electrode of the sodium ion battery and the separator, and inject the electrolyte to obtain a sodium ion battery.
需要说明的是，尽管上述步骤(a)-(d)是以特定顺序描述了钠离子电池制备方法的操作，但并非要求或者暗示必须按照该特定顺序来执行这些操作，步骤(a)、(b)、(c)和(d)的制备可以同时或者任意先后执行。It should be noted that although the above steps (a)-(d) describe the operations of the sodium ion battery preparation method in a specific order, it is not required or implied that these operations must be performed in this specific order, steps (a), ( The preparation of b), (c) and (d) can be performed simultaneously or in any order.
按照该钠离子电池的制备方法制备得到的钠离子电池具有前述钠离子电池的所有效果，在此不再赘述。The sodium ion battery prepared according to the preparation method of the sodium ion battery has all the effects of the foregoing sodium ion battery, and will not be repeated here.
根据本申请的第六个方面，提供了包括钠离子电池的设备。According to a sixth aspect of the present application, a device including a sodium ion battery is provided.
鉴于上述钠离子电池具有的优势，包含上述钠离子电池的设备，如便携式电子设备、电器设备以及电动工具等，都具有与上述钠离子电池相同的优势。In view of the advantages of the above-mentioned sodium ion battery, devices including the above-mentioned sodium ion battery, such as portable electronic equipment, electrical equipment, and power tools, have the same advantages as the above-mentioned sodium ion battery.
为了使本申请的发明目的、技术方案及其有益技术效果更加清晰，以下实施例和对比例，对本申请进行进一步详细说明。应当理解的是，本说明书中描述的实施例仅是为了解释本申请，并非为了限定本申请。本申请涉及的各原料均可通过商购获取。In order to make the invention, technical solutions and beneficial technical effects of the present application clearer, the following examples and comparative examples will further describe the present application in detail. It should be understood that the embodiments described in this specification are only for explaining this application, not for limiting this application. Each raw material involved in this application can be obtained through commercial purchase.
实施例1Example 1
一种晶体材料，化学式为Na 2Co(C 2O 4)(SO 4)·2H 2O，其制备方法包括以下步骤： A crystalline material with the chemical formula Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O. The preparation method includes the following steps:
(1)将0.710g Na 2SO 4、0.183g CoC 2O 4·2H 2O、0.504g H 2C 2O 4·2H 2O和1mL H 2O加入50mL容积水热合成反应釜； (1) Add 0.710g Na 2 SO 4 , 0.183g CoC 2 O 4 · 2H 2 O, 0.504g H 2 C 2 O 4 · 2H 2 O and 1mL H 2 O to a 50mL volume hydrothermal synthesis reactor;
(2)将装有原料的反应釜在200℃加热72小时后冷却至室温，得到Na 2Co(C 2O 4)(SO 4)·2H 2O初产物； (2) The reactor containing the raw materials was heated at 200°C for 72 hours and then cooled to room temperature to obtain Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O initial product;
(3)将Na 2Co(C 2O 4)(SO 4)·2H 2O初产物用无水乙醇超声清洗，干燥后得到纯相的Na 2Co(C 2O 4)(SO 4)·2H 2O晶体颗粒。 (3) The Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O initial product is ultrasonically cleaned with absolute ethanol and dried to obtain a pure phase of Na 2 Co(C 2 O 4 )(SO 4 )· 2H 2 O crystal particles.
实施例2Example 2
一种晶体材料，化学式为Na 2Ni(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为0.852g Na 2SO 4、0.283g NiCl 2·6H 2O和0.378g H 2C 2O 4·2H 2O，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O, the raw materials used in the preparation method are 0.852g Na 2 SO 4 , 0.283g NiCl 2 ·6H 2 O and 0.378 g H 2 C 2 O 4 · 2H 2 O, the rest is the same as in Example 1.
实施例3Example 3
一种晶体材料，化学式为Na 2Mn(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、MnC 2O 4·2H 2O和H 2C 2O 4·2H 2O，且摩尔比为6:1:2.5，其余与实施例1相同。 A crystalline material, the chemical formula is Na 2 Mn(C 2 O 4 )(SO 4 )·2H 2 O, the raw materials used in the preparation method are Na 2 SO 4 , MnC 2 O 4 · 2H 2 O and H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 6:1:2.5, the rest is the same as in Example 1.
实施例4Example 4
一种晶体材料，化学式为Na 2Cu(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、CuSO 4和H 2C 2O 4·2H 2O，且摩尔比为6:1:3.5，其余与实施例1相同。 A crystalline material, the chemical formula is Na 2 Cu(C 2 O 4 )(SO 4 )·2H 2 O, the raw materials used in the preparation method are Na 2 SO 4 , CuSO 4 and H 2 C 2 O 4 · 2H 2 O, and the molar ratio is 6:1:3.5, the rest is the same as in Example 1.
实施例5Example 5
一种晶体材料，化学式为Na 2Fe 0.5Mn 0.5(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、FeC 2O 4·2H 2O、MnC 2O 4·2H 2O和H 2C 2O 4·2H 2O，且摩尔比为4:0.5:0.5:3.5，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 )·2H 2 O. The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ·2H 2 O, MnC 2 O 4 .2H 2 O and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.5:0.5:3.5, the rest is the same as in Example 1.
实施例6Example 6
一种晶体材料，化学式为Na 2Fe 0.75Mn 0.25(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、FeC 2O 4·2H 2O、MnC 2O 4·2H 2O和H 2C 2O 4·2H 2O，且摩尔比为4:0.75:0.25:3.5，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 )·2H 2 O. The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ·2H 2 O, MnC 2 O 4 .2H 2 O and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.75:0.25:3.5, the rest is the same as Example 1.
实施例7Example 7
一种晶体材料，化学式为Na 2Fe 0.9Mn 0.1(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、FeC 2O 4·2H 2O、MnC 2O 4·2H 2O和H 2C 2O 4·2H 2O，且摩尔比为4:0.9:0.1:3.5，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O. The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ·2H 2 O, MnC 2 O 4 .2H 2 O and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.9:0.1:3.5, the rest is the same as in Example 1.
实施例8Example 8
一种晶体材料，化学式为Na 2Fe 0.9Ti 0.1(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、FeC 2O 4·2H 2O、Ti 2(SO 4) 3和H 2C 2O 4·2H 2O，且摩尔比为4:0.9:0.1:3.5，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 )·2H 2 O. The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ·2H 2 O, Ti 2 (SO 4 ) 3 and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.9:0.1:3.5, the rest is the same as in Example 1.
实施例9Example 9
一种晶体材料，化学式为Na 2Fe 0.9V 0.1(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、FeC 2O 4·2H 2O、VO 2和H 2C 2O 4·2H 2O，且摩尔比为4:0.9:0.1:3.5，反应温度为220℃，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 )·2H 2 O. The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ·2H 2 O, VO 2 and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.9:0.1:3.5, the reaction temperature is 220° C. The rest is the same as in Example 1.
实施例10Example 10
一种晶体材料，化学式为Na 2Fe 0.9Zn 0.1(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、FeC 2O 4·2H 2O、ZnSO 4和H 2C 2O 4·2H 2O，且摩尔比为4:0.9:0.1:3.5，反应温度为180℃，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O. The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ·2H 2 O, ZnSO 4 and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.9:0.1:3.5, the reaction temperature is 180° C. The rest is the same as in Example 1.
实施例11Example 11
一种晶体材料，化学式为Na 2Fe 0.9Cu 0.1(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、FeC 2O 4·2H 2O、CuSO 4和H 2C 2O 4·2H 2O，且摩尔比为4:0.9:0.1:4，反应温度为180℃，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 )·2H 2 O. The raw materials used in the preparation method are Na 2 SO 4 , FeC 2 O 4 ·2H 2 O, CuSO 4 and H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4:0.9:0.1:4, the reaction temperature is 180° C. The rest is the same as in Example 1.
实施例12Example 12
一种晶体材料，化学式为Na 2Ti 0.1Fe 0.8Mn 0.1(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、Ti 2(SO 4) 3、FeC 2O 4·2H 2O、MnC 2O 4·2H 2O和H 2C 2O 4·2H 2O，且摩尔比为8:0.1:0.8:0.1:3，反应温度为190℃，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O. The raw materials used in the preparation method are Na 2 SO 4 and Ti 2 (SO 4 ) 3 , FeC 2 O 4 · 2H 2 O, MnC 2 O 4 · 2H 2 O and H 2 C 2 O 4 · 2H 2 O, and the molar ratio is 8:0.1:0.8:0.1:3, the reaction temperature is 190 ℃, The rest is the same as in Example 1.
实施例13Example 13
一种晶体材料，化学式为Na 2Ni 0.6Mn 0.2Co 0.2(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、NiCl 2·6H 2O、MnC 2O 4·2H 2O、CoC 2O 4·2H 2O和H 2C 2O 4·2H 2O，且摩尔比为4:0.6:0.2:0.2:2，反应温度为210℃，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 )·2H 2 O. The raw materials used in the preparation method are Na 2 SO 4 , NiCl 2 ·6H 2 O, MnC 2 O 4 · 2H 2 O, CoC 2 O 4 · 2H 2 O and H 2 C 2 O 4 · 2H 2 O, and the molar ratio is 4:0.6:0.2:0.2:2, the reaction temperature is 210 ℃, the rest Same as Example 1.
实施例14Example 14
一种晶体材料，化学式为Na 2V 0.1Fe 0.8Mn 0.1(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、VO 2、FeC 2O 4·2H 2O、MnC 2O 4·2H 2O和H 2C 2O 4·2H 2O，且摩尔比为4:0.1:0.8:0.1:3，反应温度为220℃，其余与实施例1相同。 A crystalline material, the chemical formula is Na 2 V 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, the raw materials used in the preparation method are Na 2 SO 4 , VO 2 , FeC 2 O 4 · 2H 2 O, MnC 2 O 4 · 2H 2 O and H 2 C 2 O 4 · 2H 2 O, and the molar ratio is 4:0.1:0.8:0.1:3, the reaction temperature is 220 ℃, the rest is the same as Example 1 the same.
实施例15Example 15
一种晶体材料，化学式为Na 2V 0.2Fe 0.7Mn 0.1(C 2O 4)(SO 4)·2H 2O，其制备方法中所用的原料为Na 2SO 4、VO 2、FeC 2O 4·2H 2O、MnC 2O 4·2H 2O和H 2C 2O 4·2H 2O，且摩尔比为6:0.2:0.7:0.1:3.5，反应温度为180℃，其余与实施例1相同。 A crystalline material, the chemical formula is Na 2 V 0.2 Fe 0.7 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, the raw materials used in the preparation method are Na 2 SO 4 , VO 2 , FeC 2 O 4 · 2H 2 O, MnC 2 O 4 · 2H 2 O and H 2 C 2 O 4 · 2H 2 O, and the molar ratio is 6:0.2:0.7:0.1:3.5, the reaction temperature is 180 ℃, the rest is the same as Example 1 the same.
实施例16Example 16
一种晶体材料，化学式为Na 2Co(C 2O 4)(SO 4)·6H 2O，其制备方法中所用水溶剂为5mL，反应温度为100℃，其余与实施例1相同。 A crystalline material, the chemical formula is Na 2 Co(C 2 O 4 )(SO 4 )·6H 2 O, the water solvent used in the preparation method is 5 mL, the reaction temperature is 100° C, and the rest is the same as in Example 1.
实施例17Example 17
一种晶体材料，化学式为Na 2Co(C 2O 4)(SeO 4)·4H 2O，其制备方法中用相同摩尔数的硒酸钠替代硫酸钠，所用水溶剂为5mL，反应温度为120℃，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Co(C 2 O 4 )(SeO 4 )·4H 2 O. In the preparation method, sodium selenate with the same molar number is used instead of sodium sulfate, the water solvent used is 5 mL, and the reaction temperature is At 120°C, the rest is the same as in Example 1.
实施例18Example 18
一种晶体材料，化学式为Na 2Co(C 2O 4)(WO 4)·6H 2O，其制备方法中所用的原料为Na 2WO 4、CoC 2O 4·2H 2O、H 2C 2O 4·2H 2O，且摩尔比为6:1:4，反应温度为180℃，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Co(C 2 O 4 )(WO 4 )·6H 2 O, the raw materials used in the preparation method are Na 2 WO 4 , CoC 2 O 4 ·2H 2 O, H 2 C 2 O 4 ·2H 2 O, and the molar ratio is 6:1:4, the reaction temperature is 180°C, and the rest is the same as in Example 1.
实施例19Example 19
一种晶体材料，化学式为Na 2Co(C 2O 4)(S 2O 7)·2H 2O，其制备方法中所用的原料为Na 2S 2O 7、CoC 2O 4·2H 2O、H 2C 2O 4·2H 2O，且摩尔比为3.5:1:4，反应温度为150℃，所用溶剂为2mL无水乙醇，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Co(C 2 O 4 )(S 2 O 7 )·2H 2 O. The raw materials used in the preparation method are Na 2 S 2 O 7 and CoC 2 O 4 ·2H 2 O , H 2 C 2 O 4 · 2H 2 O, and the molar ratio is 3.5:1:4, the reaction temperature is 150 ℃, the solvent used is 2mL of absolute ethanol, the rest is the same as in Example 1.
实施例20Example 20
一种晶体材料，化学式为Na 2Co(C 2O 4)(HPO 4)·2H 2O，其制备方法中所用的原料为Na 2HPO 4、CoC 2O 4·2H 2O、H 2C 2O 4·2H 2O，且摩尔比为4.5:1:4，反应温度为180℃，所用溶剂为2mL无水乙醇，其余与实施例1相同。 A crystalline material with the chemical formula Na 2 Co(C 2 O 4 )(HPO 4 )·2H 2 O, the raw materials used in the preparation method are Na 2 HPO 4 , CoC 2 O 4 ·2H 2 O, H 2 C 2 O 4 .2H 2 O, and the molar ratio is 4.5:1:4, the reaction temperature is 180° C., the solvent used is 2 mL of absolute ethanol, and the rest is the same as in Example 1.
实施例21Example 21
一种钠离子半电池，正极活性材料为晶体材料，化学式为Na 2Co(C 2O 4)(SO 4)·2H 2O，粒度为500nm； A sodium ion half-cell, the positive electrode active material is a crystalline material, the chemical formula is Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O, and the particle size is 500 nm;
上述钠离子半电池的制备方法包括以下步骤：The preparation method of the above sodium ion half-cell includes the following steps:
(1)制备电池正极：将0.8g Na 2Co(C 2O 4)(SO 4)·2H 2O晶体粉末、0.1g碳黑和0.1g聚偏氟乙烯加入至2mL氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；将浆料均匀涂覆于铝箔表面(正极集流体)后真空干燥。对干燥所得电极片裁切成直径10mm的圆片，压实后作为电池正极备用； (1) Preparation of battery positive electrode: Add 0.8g Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O crystal powder, 0.1g carbon black and 0.1g polyvinylidene fluoride to 2mL of N-methylpyrrolidone solution , Fully grind to obtain a uniform slurry; apply the slurry evenly on the surface of aluminum foil (positive electrode current collector) and vacuum dry. Cut the dried electrode sheet into 10mm diameter discs and use it as a battery positive electrode after compaction;
(2)制备隔膜：将玻璃纤维薄膜裁切成直径16mm的圆片后作为隔膜备用；(2) Preparation of the diaphragm: the glass fiber film is cut into 16mm diameter discs and used as a diaphragm for backup;
(3)配制电解液：称取0.6122g高氯酸钠加入到10mL的碳酸丙烯酯，混合至高氯酸钠完全溶解，加入0.18g氟代碳酸乙烯酯作为添加剂，充分混合均匀后作为电解液备用；(3) Preparation of electrolyte: Weigh 0.6122g of sodium perchlorate and add it to 10mL of propylene carbonate, mix until the sodium perchlorate is completely dissolved, add 0.18g of fluoroethylene carbonate as an additive, mix well and use as electrolyte for standby ;
(4)制备电池负极：将金属钠于铝箔(负极集流体)上辊压成箔，将所得的钠铝复合箔裁切成直径12mm的圆片，作为电池负极备用；(4) Preparation of battery negative electrode: roll metal sodium on aluminum foil (negative electrode current collector) to form a foil, and cut the resulting sodium aluminum composite foil into a 12 mm diameter disc, which is used as a battery negative electrode;
(5)电池组装：在惰性气体保护的手套箱中，将上述制备好的电池正极、隔膜和电池负极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式电池壳体，完成电池组装。(5) Battery assembly: In an inert gas-protected glove box, the above-prepared battery positive electrode, separator and battery negative electrode are closely stacked in sequence, and the electrolyte is added dropwise to completely infiltrate the separator, and then the above-mentioned stacked part is packaged into a button battery Case, complete battery assembly.
实施例22-41Examples 22-41
一种钠离子全电池，正极活性材料和负极活性材料如表1所示：A sodium ion full battery, positive electrode active material and negative electrode active material are shown in Table 1:
表1Table 1
实施例Examples 正极活性材料Positive active material 负极活性材料Negative active material
实施例22Example 22 Na 2Co(C 2O 4)(SO 4)·2H 2O Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O 天然石墨Natural graphite
实施例23Example 23 Na 2Ni(C 2O 4)(SO 4)·2H 2O Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O 软碳Soft carbon
实施例24Example 24 Na 2Mn(C 2O 4)(SO 4)·2H 2O Na 2 Mn(C 2 O 4 )(SO 4 )·2H 2 O 球形石墨Spherical graphite
实施例25Example 25 Na 2Cu(C 2O 4)(SO 4)·2H 2O Na 2 Cu(C 2 O 4 )(SO 4 )·2H 2 O Na 2Ti 8O 17 Na 2 Ti 8 O 17
实施例26Example 26 Na 2Fe 0.5Mn 0.5(C 2O 4)(SO 4)·2H 2O Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 )·2H 2 O NaNa
实施例27Example 27 Na 2Fe 0.75Mn 0.25(C 2O 4)(SO 4)·2H 2O Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 )·2H 2 O NaNa
实施例28Example 28 Na 2Fe 0.9Mn 0.1(C 2O 4)(SO 4)·2H 2O Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O NaNa
实施例29Example 29 Na 2Fe 0.9Ti 0.1(C 2O 4)(SO 4)·2H 2O Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 )·2H 2 O NaNa
实施例30Example 30 Na 2Fe 0.9V 0.1(C 2O 4)(SO 4)·2H 2O Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 )·2H 2 O NaNa
实施例31Example 31 Na 2Fe 0.9Zn 0.1(C 2O 4)(SO 4)·2H 2O Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O NaNa
实施例32Example 32 Na 2Fe 0.9Cu 0.1(C 2O 4)(SO 4)·2H 2O Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 )·2H 2 O NaNa
实施例33Example 33 Na 2Ti 0.1Fe 0.8Mn 0.1(C 2O 4)(SO 4)·2H 2O Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O NaNa
实施例34Example 34 Na 2Ni 0.6Mn 0.2Co 0.2(C 2O 4)(SO 4)·2H 2O Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 )·2H 2 O NaNa
实施例35Example 35 Na 2V 0.1Fe 0.8Mn 0.1(C 2O 4)(SO 4)·2H 2O Na 2 V 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O 天然石墨Natural graphite
实施例36Example 36 Na 2V 0.2Fe 0.7Mn 0.1(C 2O 4)(SO 4)·2H 2O Na 2 V 0.2 Fe 0.7 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O 天然石墨Natural graphite
实施例37Example 37 Na 2Co(C 2O 4)(SO 4)·6H 2O Na 2 Co(C 2 O 4 )(SO 4 )·6H 2 O 天然石墨Natural graphite
实施例38Example 38 Na 2Co(C 2O 4)(SeO 4)·4H 2O Na 2 Co(C 2 O 4 )(SeO 4 )·4H 2 O 天然石墨Natural graphite
实施例39Example 39 Na 2Co(C 2O 4)(WO 4)·6H 2O Na 2 Co(C 2 O 4 )(WO 4 )·6H 2 O 天然石墨Natural graphite
实施例40Example 40 Na 2Co(C 2O 4)(S 2O 7)·2H 2O Na 2 Co(C 2 O 4 )(S 2 O 7 )·2H 2 O 天然石墨Natural graphite
实施例41Example 41 Na 2Co(C 2O 4)(HPO 4)·2H 2O Na 2 Co(C 2 O 4 )(HPO 4 )·2H 2 O 天然石墨Natural graphite
上述实施例22-41分别采用实施例1-20提供的晶体材料，粒度为500nm。The above examples 22-41 respectively use the crystalline materials provided in examples 1-20, and the particle size is 500 nm.
上述实施例22-41提供的钠离子全电池的制备方法，包括以下步骤：The preparation method of the sodium ion full battery provided in the above embodiments 22-41 includes the following steps:
(1)制备电池正极：将0.8g晶体粉末、0.1g碳黑和0.1g聚偏氟乙烯加入至2mL氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；将浆料均匀涂覆于铝箔表面(正极集流体)后真空干燥。对干燥所得电极片裁切成直径10mm的圆片，压实后作为电池正极备用；(1) Preparation of battery positive electrode: Add 0.8g of crystalline powder, 0.1g of carbon black and 0.1g of polyvinylidene fluoride to 2mL of N-methylpyrrolidone solution, fully grind to obtain a uniform slurry; apply the slurry evenly on the surface of aluminum foil (Positive current collector) and then vacuum dried. The dried electrode sheet is cut into 10mm diameter discs, which are used as the battery positive electrode after compaction;
(2)制备隔膜：将玻璃纤维薄膜裁切成直径16mm的圆片后作为隔膜备用；(2) Preparation of the diaphragm: the glass fiber film is cut into 16mm diameter discs and used as a diaphragm for backup;
(3)配制电解液：称取0.6122g高氯酸钠加入到10mL的碳酸丙烯酯，混合至高氯酸钠完全溶解，加入0.18g氟代碳酸乙烯酯作为添加剂，充分混合均匀后作为电解液备用；(3) Preparation of electrolyte: Weigh 0.6122g of sodium perchlorate and add it to 10mL of propylene carbonate, mix until the sodium perchlorate is completely dissolved, add 0.18g of fluoroethylene carbonate as an additive, mix well and use as electrolyte for standby ;
(4)制备电池负极：将0.8g天然石墨、0.1g碳黑和0.1g聚偏氟乙烯加入到2mL氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；将浆料均匀涂覆于铝箔表面(负极集流体)后真空干燥；对干燥所得的电极片裁切成直径10mm的圆片，压实后作为电池负极备用；(4) Preparation of battery negative electrode: Add 0.8g of natural graphite, 0.1g of carbon black and 0.1g of polyvinylidene fluoride to 2mL of N-methylpyrrolidone solution, fully grind to obtain a uniform slurry; apply the slurry evenly on the surface of aluminum foil (Negative electrode current collector) and then vacuum dried; cut the dried electrode sheet into 10mm diameter discs and compact it as a battery negative electrode;
(5)电池组装：在惰性气体保护的手套箱中，将上述制备好的电池正极、隔膜和电池负极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式电池壳体，完成电池组装。(5) Battery assembly: In an inert gas-protected glove box, the above-prepared battery positive electrode, separator and battery negative electrode are closely stacked in sequence, and the electrolyte is added dropwise to completely infiltrate the separator, and then the above-mentioned stacked part is packaged into a button battery Case, complete battery assembly.
实施例42Example 42
一种钠离子全电池，与实施例22的区别是正极晶体材料的粒度为1000nm。A sodium ion full battery is different from Example 22 in that the particle size of the positive electrode crystal material is 1000 nm.
实施例43Example 43
一种钠离子全电池，与实施例22的区别是晶体材料的制备过程中等摩尔量的CoCl 2替代CoC 2O 4·2H 2O。 Full cell one of sodium ion, and Example 22 is the difference equimolar amount of crystalline material CoCl 2 Alternative preparation of CoC 2 O 4 · 2H 2 O.
实施例44Example 44
一种钠离子全电池，与实施例22的区别是MCMB替代天然石墨。A sodium ion full battery, the difference from Example 22 is that MCMB replaces natural graphite.
对比例1Comparative Example 1
一种钠离子全电池，与实施例22的区别是正极活性材料为NaCoO 2。 A sodium ion full battery is different from Example 22 in that the positive electrode active material is NaCoO 2 .
对比例2Comparative Example 2
一种钠离子全电池，与实施例22的区别是正极活性材料为Na 3V 2(PO 4) 3。 A sodium ion full battery differs from Example 22 in that the positive electrode active material is Na 3 V 2 (PO 4 ) 3 .
对比例3Comparative Example 3
一种钠离子全电池，与实施例22的区别是正极活性材料为Na 2C 6H 2O 4。 A sodium ion full battery differs from Example 22 in that the cathode active material is Na 2 C 6 H 2 O 4 .
为进一步验证上述实施例和对比例的效果，特设以下实验例。In order to further verify the effects of the above examples and comparative examples, the following experimental examples are specially set up.
实验例1循环性能测试Experimental Example 1 Cycle performance test
对实施例21的钠离子半电池进行循环性能测试，充放电电压范围为2.0V-4.5V，充放电电流为100mA/g。图5为实施例21的钠离子电池不同循环次数下充电比容量、放电比容量和库伦效率关系图。The sodium ion half-cell of Example 21 was subjected to a cycle performance test, and the charge-discharge voltage range was 2.0V-4.5V, and the charge-discharge current was 100mA/g. 5 is a graph showing the relationship between the specific charge capacity, specific discharge capacity, and Coulomb efficiency under different cycle times of the sodium ion battery of Example 21.
由图5所示，实施例21钠离子电池的首次库伦效率为88％，充放电可逆性好，循环稳定性较好。As shown in FIG. 5, the first coulombic efficiency of the sodium ion battery of Example 21 is 88%, the reversibility of charge and discharge is good, and the cycle stability is good.
实验例2电化学性能测试Experimental Example 2 Electrochemical performance test
将实施例22-44和对比例1-3的钠离子电池进行电化学性能测试，测试结果如表2所示。The sodium ion batteries of Examples 22-44 and Comparative Examples 1-3 were subjected to electrochemical performance tests, and the test results are shown in Table 2.
测试方法如下：The test method is as follows:
1、标准充电：1. Standard charging:
环境温度30±2℃ Ambient temperature 30±2℃
恒流充电Constant current charging
恒定电流：1C，保护条件：截止电压≥4.5VConstant current: 1C, protection condition: cut-off voltage ≥ 4.5V
静置5分钟Let sit for 5 minutes
2、标准放电：2. Standard discharge:
环境温度30±2℃ Ambient temperature 30±2℃
恒流放电Constant current discharge
恒定电流：1C，保护条件：截止电压≤1.5VConstant current: 1C, protection condition: cut-off voltage ≤1.5V
静置5分钟。Let stand for 5 minutes.
稳定循环圈数是指保持初始电池容量的80％时可以循环的圈数。The number of stable cycles refers to the number of cycles that can be cycled while maintaining 80% of the initial battery capacity.
表2Table 2
实验组test group 工作电压(V)Working voltage (V) 电池容量(mAh)Battery capacity (mAh) 稳定循环圈数Number of stable cycles
实施例22Example 22 2.5-4.52.5-4.5 1.121.12 260260
实施例23Example 23 2.5-4.52.5-4.5 1.581.58 240240
实施例24Example 24 3.0-4.53.0-4.5 1.221.22 180180
实施例25Example 25 2.0-4.32.0-4.3 0.440.44 8080
实施例26Example 26 2.0-4.52.0-4.5 1.681.68 100100
实施例27Example 27 2.0-4.52.0-4.5 1.451.45 100100
实施例28Example 28 1.7-4.31.7-4.3 1.321.32 150150
实施例29Example 29 1.7-4.31.7-4.3 0.870.87 160160
实施例30Example 30 1.5-4.01.5-4.0 0.980.98 130130
实施例31Example 31 1.5-4.21.5-4.2 1.021.02 8080
实施例32Example 32 1.5-4.21.5-4.2 0.640.64 8080
实施例33Example 33 1.5-4.21.5-4.2 1.131.13 100100
实施例34Example 34 3.0-4.53.0-4.5 1.751.75 150150
实施例35Example 35 1.5-4.01.5-4.0 1.241.24 140140
实施例36Example 36 1.5-4.01.5-4.0 1.651.65 9090
实施例37Example 37 1.5-4.01.5-4.0 0.750.75 130130
实施例38Example 38 1.5-4.01.5-4.0 0.690.69 130130
实施例39Example 39 2.5-4.52.5-4.5 0.720.72 150150
实施例40Example 40 2.5-4.52.5-4.5 0.560.56 140140
实施例41Example 41 2.5-4.52.5-4.5 1.081.08 150150
实施例42Example 42 1.7-4.31.7-4.3 1.031.03 130130
实施例43Example 43 1.5-4.01.5-4.0 1.321.32 230230
实施例44Example 44 1.5-4.01.5-4.0 1.151.15 250250
对比例1Comparative Example 1 3.0-4.53.0-4.5 1.651.65 5050
对比例2Comparative Example 2 1.5-4.21.5-4.2 1.561.56 150150
对比例3Comparative Example 3 1.0-3.01.0-3.0 0.450.45 3030
从表2可以看出，本申请提供的钠离子电池的正极活性材料采用化学式为Na 2M(C 2O 4)X·nH 2O(其中M为至少一种正二价金属，X为负二价阴离子基团，0≤n≤12)的晶体材料，通过正负极的材料的相互配合，得到的钠离子全电池具有较高的工作电压、电池容量和良好的循环稳定性。 It can be seen from Table 2 that the positive electrode active material of the sodium ion battery provided in this application adopts the chemical formula Na 2 M(C 2 O 4 )X·nH 2 O (where M is at least one positive divalent metal and X is negative divalent) The valence anion group, 0≤n≤12) crystalline materials, through the coordination of the positive and negative materials, the resulting sodium ion full battery has a higher operating voltage, battery capacity and good cycle stability.
实施例26-33与实施例34的区别是正极活性材料中金属M的种类和含量不同，实施例34提供的钠离子电池的工作电压和电池容量都高于实施例26-33提供的钠离子电池，且实施例34的稳定循环圈数也较高，这表明作为正极活性材料的晶体材料中M金属元素的种类和含量会影响钠离子电池的电化学性能。The difference between Examples 26-33 and Example 34 is the type and content of metal M in the positive electrode active material. The working voltage and battery capacity of the sodium ion battery provided in Example 34 are higher than those provided in Examples 26-33 Batteries, and the stable cycle number of Example 34 is also high, which indicates that the type and content of the M metal element in the crystalline material as the positive electrode active material will affect the electrochemical performance of the sodium ion battery.
实施例35、36与实施例22的区别是正极活性材料不同，得到的钠离子电池的电化学性能有所不同，工作电压、电池容量和稳定循环圈数都有所不同。其中实施例22提供的的钠离子电池的循环性能稳定性最高，实施例22与实施例35、36提供的钠离子电池的工作电压和电池容量相差不大。The difference between Examples 35 and 36 and Example 22 is that the positive electrode active material is different, the electrochemical performance of the obtained sodium ion battery is different, and the working voltage, battery capacity and number of stable cycles are different. The sodium ion battery provided by Example 22 has the highest cycle performance stability, and the working voltage and battery capacity of the sodium ion battery provided by Example 22 and Examples 35 and 36 are not much different.
实施例37与实施例22的区别是正极活性材料的结晶水含量不同；实施例38、39与实施例22的区别均是正极活性材料的阴极离子基团和结晶水含量不同；实施例40、41与实施例22的区别均是正极活性材料的阴极离子基团不同；实施例22的钠离子电池的电化学性能比实施例37-41的钠离子电池好， 这表明正极活性材料的结晶水含量和阴离子基团的种类会影响钠离子电池的电化学性能。The difference between Example 37 and Example 22 is that the positive electrode active material has different crystal water content; the difference between Examples 38 and 39 and Example 22 is that the positive electrode active material has different cathode ion groups and crystal water content; Example 40, The difference between 41 and Example 22 is that the cathode ion group of the positive electrode active material is different; the electrochemical performance of the sodium ion battery of Example 22 is better than the sodium ion batteries of Examples 37-41, which shows that the crystalline water of the positive electrode active material The content and the type of anionic groups will affect the electrochemical performance of sodium ion batteries.
实施例42与实施例22的区别是正极活性材料的粒度不同；实施例43与实施例22的区别是制备正极活性材料的钴源不同；实施例44与实施例22的区别是负极活性材料不同。实施例22的工作电压、电池容量和稳定循环圈数都略高于实施例42；实施例22的工作电压、电池容量和稳定循环圈数与实施例43、43差异不明显，这表明正极活性材料的粒度、含金属M的原料和负极活性材料对钠离子电池的电化学性能有影响，但不显著。The difference between Example 42 and Example 22 is the particle size of the positive electrode active material; the difference between Example 43 and Example 22 is the different cobalt source for preparing the positive electrode active material; the difference between Example 44 and Example 22 is the negative electrode active material . The working voltage, battery capacity, and stable cycle number of Example 22 are slightly higher than those of Example 42; the working voltage, battery capacity, and stable cycle number of Example 22 are not significantly different from those of Examples 43 and 43, indicating positive electrode activity The particle size of the material, the raw material containing metal M and the negative electrode active material have an effect on the electrochemical performance of the sodium ion battery, but it is not significant.
对比例1与实施例22的区别是正极活性材料为含钠和钴的一种层状氧化物；对比例2与实施例22的区别是正极活性材料为一种现有的聚阴离子化合物；对比例3与实施例22的区别是正极活性材料为一种现有的有机正极材料。对比例1-3的钠离子电池的稳定循环圈数都明显不如实施例22的高，且对比例1、2的钠离子电池的工作电压和电池容量与实施例22相差不明显，对比例3的钠离子电池的工作电压和电池容量都明显低于实施例22的钠离子电池。这表明本申请提供的晶体材料制备的正极活性材料的结构稳定性高于对比例的正极活性材料。The difference between Comparative Example 1 and Example 22 is that the positive electrode active material is a layered oxide containing sodium and cobalt; the difference between Comparative Example 2 and Example 22 is that the positive electrode active material is an existing polyanion compound; The difference between Ratio 3 and Example 22 is that the positive electrode active material is an existing organic positive electrode material. The sodium-ion batteries of Comparative Examples 1-3 are obviously not as stable as those of Example 22, and the working voltage and battery capacity of the sodium-ion batteries of Comparative Examples 1 and 2 are not significantly different from that of Example 22, Comparative Example 3 The operating voltage and battery capacity of the sodium ion battery are significantly lower than the sodium ion battery of Example 22. This shows that the structural stability of the positive electrode active material prepared by the crystalline material provided in the present application is higher than that of the comparative example.
尽管已用具体实施例来说明和描述了本申请，然而应意识到，在不背离本申请的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本申请范围内的所有这些变化和修改。Although the application has been illustrated and described with specific embodiments, it should be appreciated that many other changes and modifications can be made without departing from the spirit and scope of the application. Therefore, this means that all such changes and modifications falling within the scope of the present application are included in the appended claims.

Claims (10)

  1. 一种晶体材料，其特征在于，所述晶体材料的化学式为Na 2M(C 2O 4)X·nH 2O，其中M为至少一种正二价金属，X为负二价阴离子基团，且X不为(C 2O 4)，0≤n≤12。 A crystalline material, characterized in that the chemical formula of the crystalline material is Na 2 M(C 2 O 4 )X·nH 2 O, where M is at least one positive divalent metal and X is a negative divalent anion group, And X is not (C 2 O 4 ), 0≤n≤12.
  2. 按照权利要求1所述的晶体材料，其特征在于，所述M为至少一种正二价过渡金属；The crystalline material according to claim 1, wherein the M is at least one positive divalent transition metal;
    优选地，所述M为Ti、V、Cr、Mn、Co、Ni、Cu或Zn中的至少一种，或前述至少一种金属与Fe的组合；Preferably, the M is at least one of Ti, V, Cr, Mn, Co, Ni, Cu or Zn, or a combination of at least one of the foregoing metals and Fe;
    优选地，所述X为(SO 4)、(SeO 4)、(PO 3F)、(HPO4)、(HAsO 4)、(MoO 4)、(WO 4)、(S 2O 7)或(Se 2O 7)阴离子基团中的一种，0≤n≤6； Preferably, X is (SO 4 ), (SeO 4 ), (PO 3 F), (HPO4), (HAsO 4 ), (MoO 4 ), (WO 4 ), (S 2 O 7 ) or ( Se 2 O 7 ) one of the anionic groups, 0≤n≤6;
    优选地，所述晶体材料的化学式为Na 2Co(C 2O 4)(SO 4)·2H 2O、Na 2Ni(C 2O 4)(SO 4)·2H 2O、Na 2Mn(C 2O 4)(SO 4)·2H 2O、Na 2Cu(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.5Mn 0.5(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.75Mn 0.25(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Ti 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9V 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Zn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Fe 0.9Cu 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Ti 0.1Fe 0.8Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Ni 0.6Mn 0.2Co 0.2(C 2O 4)(SO 4)·2H 2O、Na 2V 0.1Fe 0.8Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2V 0.2Fe 0.7Mn 0.1(C 2O 4)(SO 4)·2H 2O、Na 2Co(C 2O 4)(SO 4)·6H 2O、Na 2Co(C 2O 4)(SeO 4)·2H 2O、Na 2Fe(C 2O 4)(SeO 4)·4H 2O、Na 2Fe(C 2O 4)(WO 4)·6H 2O、Na 2Fe(C 2O 4)(S 2O 7)·2H 2O或Na 2Fe(C 2O 4)(HPO 4)·2H 2O中的一种。 Preferably, the chemical formula of the crystalline material is Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Mn( C 2 O 4 )(SO 4 )· 2H 2 O, Na 2 Cu(C 2 O 4 )(SO 4 )· 2H 2 O, Na 2 Fe 0.5 Mn 0.5 (C 2 O 4 )(SO 4 )· 2H 2 O, Na 2 Fe 0.75 Mn 0.25 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 Ti 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 V 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Fe 0.9 Zn 0.1 (C 2 O 4 )( SO 4 )·2H 2 O, Na 2 Fe 0.9 Cu 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Ti 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Ni 0.6 Mn 0.2 Co 0.2 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 V 0.1 Fe 0.8 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 V 0.2 Fe 0.7 Mn 0.1 (C 2 O 4 )(SO 4 )·2H 2 O, Na 2 Co(C 2 O 4 )(SO 4 )·6H 2 O, Na 2 Co(C 2 O 4 )(SeO 4 )·2H 2 O, Na 2 Fe(C 2 O 4 )(SeO 4 )·4H 2 O, Na 2 Fe(C 2 O 4 )(WO 4 )·6H 2 O, Na 2 Fe(C 2 O 4 ) (S 2 O 7 )· 2H 2 O or Na 2 Fe(C 2 O 4 )(HPO 4 )· 2H 2 O.
  3. 按照权利要求1或2所述的晶体材料，其特征在于，所述晶体材料的化学式为Na 2Co(C 2O 4)(SO 4)·2H 2O，属于六方晶系，空间群为P-63m，失水温度为180℃，分解温度为300℃，单胞参数为
    Figure PCTCN2018122244-appb-100001
    α＝β＝90°，γ＝120°，
    Figure PCTCN2018122244-appb-100002
    Z＝1；     The crystalline material according to claim 1 or 2, wherein the chemical formula of the crystalline material is Na 2 Co(C 2 O 4 )(SO 4 )·2H 2 O, which belongs to the hexagonal crystal system and the space group is P -63m, water loss temperature is 180℃, decomposition temperature is 300℃, unit cell parameter is
    Figure PCTCN2018122244-appb-100001
    α=β=90°, γ=120°,
    Figure PCTCN2018122244-appb-100002
    Z=1;
    优选地，所述晶体材料的化学式为Na 2Ni(C 2O 4)(SO 4)·2H 2O，属于六方晶系，空间群为P-63m，失水温度为180℃，分解温度为310℃，单胞参数为
    Figure PCTCN2018122244-appb-100003
    α＝β＝90°，γ＝120°，
    Figure PCTCN2018122244-appb-100004
    Z＝1。     Preferably, the chemical formula of the crystalline material is Na 2 Ni(C 2 O 4 )(SO 4 )·2H 2 O, which belongs to the hexagonal crystal system, the space group is P-63m, the water loss temperature is 180°C, and the decomposition temperature is 310℃, the unit cell parameter is
    Figure PCTCN2018122244-appb-100003
    α=β=90°, γ=120°,
    Figure PCTCN2018122244-appb-100004
    Z=1.
  4. 一种权利要求1-3任一项所述晶体材料的制备方法，其特征在于，包括以下步骤：将钠源、M源、草酸根源、X源和溶剂混合均匀后进行溶剂热反应，得到晶体材料；A method for preparing a crystalline material according to any one of claims 1 to 3, characterized in that it comprises the steps of mixing sodium source, M source, oxalate source, X source and solvent uniformly, and then performing a solvothermal reaction to obtain crystals material;
    优选地，所述钠源、M源、草酸根源和X源的摩尔比为(2-8):1:(1-8):(2-8)；Preferably, the molar ratio of the sodium source, the M source, the oxalate source and the X source is (2-8): 1: (1-8): (2-8);
    优选地，所述钠源包括含钠的氧化物、碱或盐中的至少一种；Preferably, the sodium source includes at least one of oxides, bases or salts containing sodium;
    优选地，所述M源包括含M的氧化物、酸、碱、盐或M单质中的至少一种；Preferably, the M source includes at least one of M-containing oxides, acids, bases, salts, or M elements;
    优选地，所述草酸根源包括含草酸根的酸或盐中的至少一种；Preferably, the oxalate source includes at least one of oxalate-containing acid or salt;
    优选地，所述X源包括含X的酸或盐中的至少一种；Preferably, the X source includes at least one of X-containing acids or salts;
    优选地，所述溶剂为水、醇类、酮类或吡啶类中的至少一种，优选水。Preferably, the solvent is at least one of water, alcohols, ketones or pyridines, preferably water.
  5. 按照权利要求4所述的晶体材料的制备方法，其特征在于，所述溶剂热的温度为100-300℃，时间为4-100h；The method for preparing a crystalline material according to claim 4, wherein the solvothermal temperature is 100-300°C and the time is 4-100h;
    优选地，所述溶剂热的温度为180-220℃，时间为48-72h。Preferably, the solvothermal temperature is 180-220°C and the time is 48-72h.
  6. 权利要求1-3任一项所述的晶体材料，或权利要求4或5所述的晶体材料的制备方法制备得到的晶体材料在制备正极活性材料中的应用。Use of the crystalline material according to any one of claims 1 to 3, or the crystalline material prepared by the method for preparing a crystalline material according to claim 4 or 5 in preparing a positive electrode active material.
  7. 一种钠离子电池正极材料，其特征在于，包含权利要求1-3任一项所述的晶体材料，或权利要求4或5所述的晶体材料的制备方法制备得到的晶体材料。A positive electrode material for sodium ion battery, characterized by comprising the crystalline material according to any one of claims 1-3, or the crystalline material prepared by the method for preparing a crystalline material according to claim 4 or 5.
  8. 按照权利要求7所述的钠离子电池正极材料，其特征在于，包括正极活性材料、正极导电剂和正极粘结剂；正极活性材料、正极导电剂和正极粘结剂的重量比为(60-90):(5-30):(3-10)；所述正极活性材料为所述的晶体材料；The positive electrode material for a sodium ion battery according to claim 7, characterized in that it comprises a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; the weight ratio of the positive electrode active material, the positive electrode conductive agent and the positive electrode binder is (60- 90): (5-30): (3-10); the positive electrode active material is the crystalline material;
    优选地，所述正极导电剂包括导电炭黑、导电碳球、导电石墨、导电碳纤维、碳纳米管、石墨烯或还原氧化石墨烯中的至少一种；Preferably, the positive electrode conductive agent includes at least one of conductive carbon black, conductive carbon balls, conductive graphite, conductive carbon fibers, carbon nanotubes, graphene or reduced graphene oxide;
    优选地，所述正极粘结剂包括聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、丁苯橡胶或聚烯烃类中的至少一种。Preferably, the positive electrode binder includes at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene-butadiene rubber or polyolefin.
  9. 一种钠离子电池，其特征在于，包括权利要求7或8所述的钠离子电池正极材料。A sodium ion battery, characterized by comprising the positive electrode material of sodium ion battery according to claim 7 or 8.
  10. 包括权利要求9所述的钠离子电池的设备。A device comprising the sodium ion battery of claim 9.
PCT/CN2018/122244 2018-12-20 2018-12-20 Crystal material, preparation method and use thereof, positive electrode material for sodium ion battery, sodium ion battery, and apparatus WO2020124468A1 (en)

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CN102132444A (en) * 2008-08-27 2011-07-20 住友化学株式会社 Electrode active material and method for producing same
US20150333325A1 (en) * 2012-11-19 2015-11-19 Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University) Manufacturing method of positive active material precursor for sodium rechargeable batteries, positive active material precursor for sodium rechargeable batteries made by the same, and manufacturing method of positive active material for sodium rechargeable batteries, positive active material for sodium rechargeable batteries made by the same
CN105789617A (en) * 2016-05-17 2016-07-20 西南大学 Preparation method of sodium-ion battery cathode material as well as product and application of sodium-ion battery cathode material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102132444A (en) * 2008-08-27 2011-07-20 住友化学株式会社 Electrode active material and method for producing same
US20150333325A1 (en) * 2012-11-19 2015-11-19 Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University) Manufacturing method of positive active material precursor for sodium rechargeable batteries, positive active material precursor for sodium rechargeable batteries made by the same, and manufacturing method of positive active material for sodium rechargeable batteries, positive active material for sodium rechargeable batteries made by the same
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