WO2013155964A1 - Battery - Google Patents

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Publication number
WO2013155964A1
WO2013155964A1 PCT/CN2013/074304 CN2013074304W WO2013155964A1 WO 2013155964 A1 WO2013155964 A1 WO 2013155964A1 CN 2013074304 W CN2013074304 W CN 2013074304W WO 2013155964 A1 WO2013155964 A1 WO 2013155964A1
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WO
WIPO (PCT)
Prior art keywords
positive electrode
current collector
battery
electrolyte
mesh
Prior art date
Application number
PCT/CN2013/074304
Other languages
French (fr)
Chinese (zh)
Inventor
陈璞
颜竞
Original Assignee
苏州宝时得电动工具有限公司
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Publication of WO2013155964A1 publication Critical patent/WO2013155964A1/en

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Classifications

    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • 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 invention belongs to the field of electrochemical energy storage, and particularly relates to a battery.
  • lithium secondary batteries have many advantages compared with conventional nickel-hydrogen and nickel-cadmium secondary batteries, such as high energy density and light weight, which can be applied to portable electronic products such as notebook computers; Low self-discharge, long cycle life, no memory effect, can be charged and discharged multiple times; Wide operating temperature, can be used in many extreme environments; Good safety performance, no gas generated during work; No environmental pollution, Conducive to environmental protection, etc. .
  • the present invention is directed to a battery having good electrochemical performance and high energy density.
  • the present invention provides a battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising a positive electrode current collector and a coating layer formed on the positive electrode current collector, the coating layer comprising at least a positive electrode active material participating in a positive electrode reaction,
  • the positive electrode active material is capable of reversibly extracting-embeding ions;
  • the negative electrode includes at least a negative electrode current collector;
  • the electrolyte solution includes a solvent and an electrolyte, and the solvent is selected from water or alcohol, and the electrolyte is at least capable of being ionized during charging and discharging.
  • Reactive-deposited and oxidized-dissolved active ions are generated in the negative electrode; the areal density of the positive active material in the coating ranges from 100 to 3000 g/m 2 .
  • the surface active density of the positive electrode active material in the coating layer is from 300 to 1 500 g/m 2 .
  • the thickness of the coating ranges from 40 to 1000 ⁇ m.
  • the present invention also provides a battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising a positive electrode current collector and a coating layer formed on the positive electrode current collector, the coating layer comprising at least a positive electrode active material participating in a positive electrode reaction
  • the positive active material is capable of reversibly extracting-embeding ions
  • the negative electrode includes at least a negative current collector
  • the electrolyte includes a solvent and an electrolyte, and the solvent is selected from water or alcohol.
  • the electrolyte is capable of at least ionizing reactive ions that undergo reduction-deposition and oxidation-dissolution at the negative electrode during charge and discharge; the thickness of the coating ranges from 40 to 1000 ⁇ m.
  • the positive electrode active material accounts for 60-99% of the specific gravity of the coating layer.
  • the coating further includes a conductive agent, and the conductive agent accounts for a specific gravity range of the coating.
  • the coating further comprises a binder, the binder having a specific gravity ranging from 0.5 to 10%.
  • the positive electrode current collector has a thickness ranging from 5 to 100 ⁇ m.
  • the material of the cathode current collector is selected from one of a carbon-based material, a metal or an alloy, wherein the carbon-based material is selected from the group consisting of glassy carbon, graphite foil, foamed carbon, carbon felt, and carbon fiber.
  • the metal is selected from the group consisting of Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or a passivated one of the above metals;
  • the alloy is selected from the group consisting of stainless steel, Al alloy, One of a Ni alloy, a Ti alloy, a Cu alloy, a Co alloy, a Ti-Pt alloy, a Pt-Rh alloy, or a passivated alloy.
  • the cathode current collector is a stainless steel mesh
  • the size of the stainless steel mesh is selected from the group consisting of 100 mesh, 10 mesh, 120 mesh, 150 mesh, 160 mesh, 180 mesh, 200 mesh, 250 mesh, and 270 mesh 300 mesh.
  • the cathode current collector is a passivated stainless steel mesh.
  • the battery provided by the invention has the surface density of the positive active material in the coating set to 100-3000 g/m 2 , and the battery has excellent electrochemical performance, high energy density and good cycle performance, safe battery operation and low production cost. It is suitable as an energy storage system for large-scale energy storage and as an alternative to lead-acid batteries.
  • FIG. 1 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 1.
  • FIG. 2 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 2.
  • FIG. 4 is a graph showing the relationship between the coulombic efficiency and the number of cycles of the battery provided in Example 3;
  • FIG. 7 is a graph showing the relationship between the coulombic efficiency and the number of cycles of the battery provided in Example 5;
  • FIG. 9 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 8.
  • a battery that can be applied to portable electronic products such as mobile phones and notebook computers, electric cars, electric tools, and the like.
  • a battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising a positive electrode current collector and a coating formed on the positive electrode current collector, the coating layer comprising at least a positive electrode active material participating in the positive electrode reaction.
  • the positive electrode active material accounts for 60-99% by weight of the coating layer, and the surface density of the positive electrode active material in the coating ranges from 100 to 3000 g/m 2 .
  • the surface density of the positive electrode active material in the coating ranges from 300 to 300- 1500 g/m 2 , coating thickness ranging from 40 to 1000 ⁇ m.
  • the invention also provides a battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising a positive electrode current collector and a coating formed on the positive electrode current collector, the coating layer comprising at least a positive electrode active material participating in the positive electrode reaction, and the coating thickness ranges from 40-1000 ⁇ .
  • the coating dry-formed positive electrode is subjected to pressing treatment, and the thickness of the coating after the pressing treatment ranges from 40 to 1000 ⁇ m, and the coating has no dry cracking or powder falling phenomenon, and the positive electrode is manufactured according to the design. Has excellent electrochemical properties.
  • the positive electrode active material is capable of reversibly extracting - intercalating ions.
  • the positive electrode active material is capable of reversibly extracting - intercalating lithium ions, sodium ions or magnesium ions.
  • the positive electrode active material is a compound capable of reversibly deintercalating-intercalating lithium ion-doped spinel structure conforming to the general formula Li 1+x Mn y M z O k , wherein -l ⁇ x ⁇ 0.5, 1 ⁇ y ⁇ 2.5, 0 ⁇ z ⁇ 0.5, 3 ⁇ k ⁇ 6, M is at least one selected from the group consisting of Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, and Al t .
  • the positive electrode active material contains LiMn 2 0 4 . More preferably, the positive active material contains LiMn 2 0 4 which is doped or coated modified.
  • the positive active material is a compound capable of reversibly deintercalating-intercalating lithium ion in a layered structure conforming to the general formula Li l+ x M y M' z M" c 02 + n, wherein -l ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1 , 0 ⁇ c ⁇ 1 , -0.2 ⁇ n ⁇ 0.2, M, ⁇ ', ⁇ " are respectively selected from Ni, Mn, Co, Mg, Ti, Cr, V At least one of Zn, Zr, Si or Al.
  • the positive electrode active material contains LiCo0 2 .
  • the positive active material is a compound capable of reversibly deintercalating-intercalating lithium ion olivine structure according to the general formula Li x M ⁇ y M' y (X0 4 ) n , wherein 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 0.6, 1 ⁇ n ⁇ 1.5, M is selected from Fe, Mn, V or Co, and M' is at least one selected from the group consisting of Mg, Ti, Cr, V or Al, and X is selected from S, P or Si. At least one of them.
  • the positive electrode active material contains LiFePO 4 .
  • LiFeP0 4 and LiCo0 2 should also be broadly understood to include modifications through various doping, cladding, etc., which are in accordance with Li x M 1 -y M' y (X0 4 ) n and Li 1 + , respectively.
  • the positive electrode active material is a lithium ion elution-embedded compound
  • a compound such as LiMn 2 0 4 , LiFeP0 4 , LiCo0 2 , LiM x P0 4 , LiM x SiO y (wherein M is a variable metal) may be used.
  • the compound NaVP0 4 F which can be eluted-inserted with sodium ions can be eluted-embedded into the magnesium ion compound MgM x O y (where M is a metal, 0.5 ⁇ X ⁇ 3, 2 ⁇ y ⁇ 6) and has similar functions.
  • a compound capable of deintercalating-embedding an ion or a functional group can be used as a positive electrode active material of the battery of the present invention, and therefore, the present invention is not limited to a lithium ion battery.
  • the coating further includes a conductive agent, and the conductive agent mainly serves to improve the conductivity of the coating, and the conductive agent accounts for 0.5-30% by weight of the coating.
  • the conductive agent includes at least one selected from the group consisting of a conductive polymer, carbon nanotubes, activated carbon, graphene, carbon black, and carbon fibers.
  • Carbon black includes, but is not limited to, acetylene black, Ketjen black (KB), and super-p carbon black.
  • the coating further comprises a binder, the binder is mainly a polymer compound for adhering the active material to the current collector, enhancing the electronic contact between the active material and the conductive agent and the active material and the current collector, thereby better stabilizing the positive electrode. Performance.
  • the binder accounts for 0.5 to 10% by weight of the coating.
  • the binder is selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose derivative (CMC derivation), and styrene butadiene rubber (SBR). At least one of a styrene-butadiene rubber derivative (SBR derivation).
  • a styrene-butadiene rubber derivative such as a hydrophilic styrene-butadiene rubber (PSBR100) obtained by chemical modification.
  • the positive electrode current collector is mainly used as a carrier for conducting and collecting electrons, and the material of the positive electrode current collector includes one of a carbon-based material, a metal or an alloy.
  • the carbon-based material is selected from the group consisting of glassy carbon, graphite foil, foamed carbon, carbon felt, and carbon fiber.
  • the positive current collector is graphite, such as a commercial graphite pressed foil, wherein the weight ratio of graphite ranges from 90 to 100%.
  • the metal is a metal mesh or a metal foil, and the metal includes one of Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the above-mentioned metal which has been passivated.
  • the positive current collector is selected from the group consisting of passivated aluminum foil.
  • the main purpose of passivating the metal is to form a passivation film on the surface of the metal. During the charging and discharging process of the battery, it can stably collect and conduct electrons, and does not participate in the positive electrode reaction to ensure battery performance.
  • the alloy includes one of stainless steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-h alloy or passivated.
  • Stainless steel includes stainless steel mesh, stainless steel foil, and stainless steel models include, but are not limited to, stainless steel 304 or stainless steel 3 16 or stainless steel 3 16L.
  • the positive current collector is a stainless steel foil of the type 304. If the cathode current collector is made of stainless steel mesh, the specification range of the stainless steel mesh is selected from 100 mesh, 10 mesh, 120 mesh, 150 mesh, 160 mesh, 180 mesh, 200 mesh, 250 mesh, 270 mesh or 300 mesh, preferably The stainless steel mesh has a size of 150 mesh, and the positive electrode active material can be stably coated on the surface of the positive electrode current collector to facilitate the progress of the positive electrode reaction.
  • the coating may be applied on both sides of the positive current collector, or the coating may be applied on only one side.
  • the positive current collector is stainless steel.
  • Mesh or foil, coated on both sides of a stainless steel mesh or stainless steel foil, and either side of the stainless steel mesh or stainless steel foil is a single layer coating.
  • the thickness of the single layer coating ranges from 40 to 1000 ⁇ m.
  • the passivation treatment of stainless steel also enables it to stably collect and conduct electrons without participating in the positive electrode reaction to ensure battery performance.
  • the specific process of passivating the stainless steel is: placing the stainless steel in 20% nitric acid at 50 ° C for half an hour to form a passivation film on the surface of the stainless steel.
  • the passivated stainless steel is used as a current collector.
  • the thickness of the positive current collector has a certain influence on the electrochemical performance of the positive electrode.
  • the thickness of the positive current collector is too thin, which will affect the mechanical strength of the positive current collector.
  • the thickness of the positive current collector is too thick, which will increase the weight of the positive electrode and affect the positive electrode.
  • Energy density in the present invention, the thickness of the positive electrode current collector is 5 - 100 ⁇ , and in a preferred embodiment, the thickness of the positive electrode current collector is 50 ⁇ .
  • the negative electrode includes at least a negative current collector, and in one negative electrode embodiment, the negative electrode includes only the negative current collector.
  • the anode current collector acts only as a carrier for electron conduction and collection and does not participate in the electrochemical reaction.
  • the material of the negative current collector is selected from at least one of the metals Ni, Cu, Ag, Pb, Sn, Fe, Al or the passivated metal, or a carbon-based material, or stainless steel.
  • carbon-based materials include graphite materials, such as commercial graphite-pressed foils, in which graphite accounts for 90-100% by weight.
  • Stainless steel materials include, but are not limited to, stainless steel 304 or stainless steel 3 16 or stainless steel 3 16L.
  • the anode current collector may also be selected from a metal containing a plating/coating having a high hydrogen evolution potential, thereby reducing the occurrence of negative side reactions.
  • the plating/coating is selected from the group consisting of C, Sn, In, Ag, Pb, Co, and Zn. Gold, or at least one of oxides.
  • the thickness of the plating/coating ranges from 1 to 1000 nm.
  • the surface of the negative current collector of copper is plated with lead or silver, or coated with a layer of carbon.
  • the electrolyte includes a solvent and at least one electrolyte, and the solvent includes at least one of an aqueous solution or an alcohol solution including, but not limited to, ethanol or methanol.
  • the electrolyte is capable of ionizing reactive ions which undergo reduction-deposition and oxidation-dissolution at the negative electrode during charge and discharge.
  • the living ions include metal ions selected from at least one of Zn, Fe, Cr, Cu, Mn, and Ni.
  • the reactive ion is Zn 2+ .
  • the concentration of the active ions ranges from 0.5 to 15 mol/L.
  • the metal ion is present in the electrolyte in one or more of a chlorate, a tetra-acid salt, a nitrate salt, an acetate salt, a formate salt, or a phosphate.
  • the metal ions are present in the electrolyte in the form of sulfate or nitrate or acetate; when the cathode current collector is passivated metal aluminum, preferably, metal The ions are present in the electrolyte in the form of sulfate or acetate.
  • the electrolyte further includes an electrolyte which can be ionized to correspond to ions capable of reversible elution-embedding at the positive electrode.
  • the electrolyte contains reversible elution-embedded ions, so that the ion exchange rate between the positive electrode active material and the electrolyte can be increased.
  • the positive electrode active material is a compound capable of reversibly deintercalating-intercalating lithium ions
  • the electrolyte further includes lithium ions.
  • the embedded ions include lithium ions or sodium ions or magnesium ions, and the reversible deionization-embedded ions have a concentration in the electrolyte ranging from 0.1 to 1 mol/L.
  • the electrolyte comprises lithium, zinc, nitric acid, sulfuric acid or acetate.
  • the concentration of active ions in the electrolyte must reach a certain range.
  • the electrolyte is over-alkali, it will affect the solubility of the active ions in the electrolyte; when the electrolyte is too acidic, the electrode material will corrode and charge. Problems such as proton embedding during discharge, therefore, the pH of the electrolyte ranges from 3 -7.
  • the charging and discharging principle of the battery is as follows: During charging, the reversible elution-embedded ions are removed from the positive active material, and at the same time, the metal in the positive active material is oxidized and the electrons are released; the electrons reach the negative electrode of the battery through the external circuit, and at the same time in the electrolyte The active ions are reduced at the negative electrode and deposited on the negative electrode.
  • the discharge process is the reverse process of charging.
  • the battery uses an aqueous solution electrolyte, there is no safety hazard such as flammability of the organic electrolyte, and the aqueous electrolyte has higher ionic conductivity than the organic electrolyte, which reduces the influence of battery polarization. Therefore, the battery provided by the present invention
  • the surface active density of the positive active material in the coating ranges from 100 to 3000 g/m 2 . This allows the battery to have a very large specific capacity and energy while having very excellent electrochemical performance.
  • the negative electrode includes only the negative current collector, and the material of the negative current collector corresponds to the active ion in the electrolyte, that is, the material of the negative current collector is a simple substance of the active ion, such as the active ion in the electrolyte.
  • the negative electrode corresponds to metal Zn.
  • the negative electrode is not only a deposition carrier as a living ion, but also participates in a battery reaction.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material, and the material of the negative electrode active material corresponds to the active ion in the electrolyte, that is, the material of the negative electrode active material is a simple substance of the active ion, such as an active substance in the electrolyte.
  • the ion is Zn 2+
  • the negative electrode active material corresponds to metal Zn.
  • the battery provided by the present invention may be provided with a separator during the manufacturing process, and the separator comprises an organic or inorganic porous material having a porosity ranging from 20 to 95% and a pore diameter ranging from 0.001 to 100 ⁇ m.
  • the battery provided by the present invention has an areal density of the positive electrode active material in the coating ranging from 100 to 3000 g/m 2 , and preferably, the areal active material has an areal density of 300 to 1500 g/m 2 , so that the battery to which the coating is applied has Good electrochemical performance, and the battery exhibits excellent cycle performance during charge and discharge. Therefore, the battery of the present invention has great application potential in low voltage applications such as lead storage batteries and alkaline zinc manganese batteries.
  • a battery the current collector of the battery is made of a stainless steel rod of size 304
  • the active material of the positive electrode coating is LiMn 2 0 4
  • the surface density of LiMn 2 0 4 is 500 g/m 2
  • the negative electrode is made of stainless steel rod of size 304.
  • the electrolytic solution was a mixed aqueous solution of 1 mol/L of lithium acetate and 1.5 mol/L of zinc acetate.
  • Figure 1 shows the relationship between the discharge capacity of the battery and the number of cycles. It can be seen from the figure that the initial discharge capacity of the battery is 5 mAh, and the specific capacity based on the positive electrode material is 100 mAh/g. After 200 charge and discharge, the capacity remains at 90. Above %, has a very high capacity retention rate.
  • a battery the current collector of the battery is made of stainless steel rod of size 304, the active material of the positive electrode coating layer is LiMn 2 0 4 , the surface density of LiMn 2 0 4 is 300 g/m 2 , and the negative electrode is made of stainless steel rod of specification 304.
  • the electrolytic solution was a mixed aqueous solution of 3 mol/L of lithium acetate and 1.5 mol/L of zinc acetate.
  • Figure 1 is a diagram showing the relationship between the discharge capacity of the battery and the number of cycles. As can be seen from the figure, the battery is initially placed. The capacity is 3 mAh, the specific capacity based on the positive electrode material is 100 mAh/g, and the capacity efficiency after the battery is cycled for 160 weeks is still more than 80%. The results show that the battery has excellent discharge performance and cycle performance.
  • LiL05M .89Coo.03Alo.03O4 was used as the positive electrode active material, and the positive electrode active material, binder P VDF, super-p carbon black were mixed in a weight ratio of 83:10:7 and dissolved in N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • a positive electrode slurry is prepared in which a positive electrode current collector is a graphite plate having a thickness of 1 mm, and a positive electrode slurry is uniformly coated on a positive electrode current collector.
  • the surface active density of the positive electrode active material in the positive electrode material is 170 g/m 2 , and the coating thickness is 40 um. It was dried in air at 110 ° C for 24 hours to form a positive electrode.
  • the battery anode current collector is a stainless steel rod.
  • the electrolytic solution was a deionized aqueous solution containing a concentration of 4 mol/L of zinc chloride and 3 mol/L of lithium chloride, and the pH of the electrolytic solution was adjusted to 4 by titrating 0.1 mol/L of lithium hydroxide into the electrolytic solution.
  • the diaphragm is a glass felt cloth.
  • the positive electrode and the negative electrode were assembled into a battery, and the separator was partitioned therebetween to inject an electrolyte solution. After the battery was assembled, it was allowed to stand for 12 hours and then charged and discharged at a 4 C rate.
  • the charge and discharge voltage range is 1.5-2. IV.
  • Example 3 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 3. As is clear from the figure, the discharge capacity of the battery cycle 4000 times is almost equal to the first discharge capacity, and the battery not only has a very stable cycle performance, but also has a cycle. long life.
  • Example 4 is a graph showing the Coulomb efficiency and the number of cycles of the battery provided in Example 3. It can be seen from the figure that the coulombic efficiency is still close to 100% after the battery cycle 4000 times, indicating that the charge and discharge performance of the battery of the present invention is very stable. .
  • LiMn 2 0 4 as a positive electrode active material, the positive electrode active material, the binder polytetrafluoroethylene (PTFE), and the super-p carbon black were mixed at a ratio of 83:10:7 and dissolved in N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • the surface active density of the positive electrode active material was 800 g/m 2 , and the thickness of the coating layer was 0.5 mm.
  • the positive electrode current collector was a stainless steel mesh having a thickness of 30 ⁇ m, and the stainless steel was not passivated.
  • the positive electrode slurry was uniformly coated on the positive electrode current collector, and dried in air at 110 ° C for 24 hours to prepare a positive electrode.
  • the negative electrode current collector of the battery is a copper foil having a thickness of ⁇ .
  • the electrolyte is an aqueous solution containing a concentration of 1 mol/L lithium acetate and 1.5 mol/L zinc acetate.
  • the pH of the electrolyte is adjusted to 4 by titrating 0.1 mol/L lithium hydroxide and 0.1 mol/L HAc into the electrolyte. .
  • the diaphragm is a glass felt cloth.
  • the positive electrode and the negative electrode were assembled into a battery, and the separator was partitioned therebetween to inject an electrolyte solution. After the battery was assembled, it was allowed to stand for 12 hours and then charged and discharged at a rate of 0.5 C.
  • the charge and discharge voltage range is 1.5-2. IV.
  • Fig. 5 is a graph showing the discharge capacity of the battery of Example 4 as a function of the number of cycles. From the picture It is clear that the first discharge capacity of the battery is that the discharge capacity after the cycle of 250 times is almost the same as the first discharge capacity, indicating that the cycle performance of the battery is very stable, and the battery provided by the present invention has excellent electrochemical performance.
  • LiMn 2 0 4 is used as a positive electrode active material, and a positive electrode active material, super-p carbon black, and a binder PVDF are uniformly mixed in a weight ratio of 83:10:7, and a positive electrode slurry is prepared by using NMP as a dispersing agent.
  • the positive electrode current collector graphite foil was coated on a thickness of 80 ⁇ m, and the surface active density of the positive electrode active material was 300 g/m 2 , followed by drying and pressing to obtain a positive electrode.
  • the negative electrode is a metal zinc foil having a thickness of 50 ⁇ m, and the metal zinc is both a negative electrode active material and also serves as a negative electrode current collector.
  • the separator is a non-woven fabric.
  • the electrolytic solution was an aqueous solution containing 3 mol/L of lithium chloride and 4 mol/L of zinc chloride, and the pH of the electrolytic solution was adjusted to 4 by dropwise addition of 0.1 mol/L of LiOH solution to the electrolytic solution.
  • the battery was charged and discharged at a rate of 1 C in a voltage range of 1.5 to 2.1 V at room temperature.
  • Fig. 6 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 5. The battery was slightly attenuated after 30 cycles, but the decay rate was very slow.
  • Figure 7 is a graph showing the Coulomb efficiency versus the number of cycles for the battery provided in Example 5. The coulombic efficiency of the battery after 30 cycles was nearly 90%.
  • LiMn 2 0 4 was used as a positive electrode active material, and a positive electrode active material, super-p carbon black, and a binder CMC-SB were uniformly mixed in a weight ratio of 83:10:7, and NMP was used as a dispersing agent to prepare a positive electrode slurry.
  • the coating was applied to a positive electrode current collector stainless steel foil having a thickness of 50 ⁇ m.
  • the surface active density of the positive electrode active material was 700 g/m 2 and the coating thickness was 0.4 mm.
  • the stainless steel was not passivated, and then dried and pressed to obtain a positive electrode.
  • the negative electrode is a metal zinc foil having a thickness of 40 ⁇ m, and the metal zinc is both a negative electrode active material and also serves as a negative electrode current collector.
  • the diaphragm is a glass felt cloth.
  • the electrolyte is an aqueous solution containing 1 mol/L of lithium acetate and 1.5 mol/L of zinc acetate, and the electrolyte is adjusted by adding 0.1 mol/L of LiOH and 0.1 mol/L of HAc solution to the electrolyte.
  • the pH is 4.
  • the battery was charged and discharged at a rate of 0.5 C in a voltage range of 1.5 to 2.1 V at room temperature.
  • Example 6 The battery experiment results in Example 6 showed that the discharge capacity retention rate and the coulombic efficiency of the battery cycle were close to 100%, indicating that the battery has excellent cycle performance and longevity.
  • Example 7 the battery was charged and discharged at 55 ° C to investigate the charge and discharge performance of the battery at a high temperature.
  • the other compositions and test methods of the battery were the same as those in Example 6.
  • 8 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 7. As can be seen from the figure, the battery still has a good discharge capacity retention rate at a high temperature of 55 ° C, and the battery cycle is almost no significant 160 times. The capacity is attenuated.
  • LiMn 2 0 4 was used as the positive electrode active material, and the positive electrode active material, super-p carbon black, and the binder PVDF were uniformly mixed at a weight ratio of 83:10:7, and NMP was used as a dispersing agent to prepare a positive electrode slurry, which was uniformly coated.
  • the positive electrode active material has a surface density of 300 g/m 2 and a thickness of 0.2 mm.
  • the stainless steel is not passivated, and then dried and pressed to obtain a positive electrode.
  • the negative electrode is a metal zinc foil having a thickness of ⁇ , which is both a negative electrode active material and also serves as a negative electrode current collector.
  • the diaphragm is a glass felt cloth.
  • the electrolyte was an aqueous solution containing 1 mol/L of lithium acetate and 1.5 mol/L of zinc acetate, and the pH of the electrolyte was adjusted to 4 by dropwise addition of 0.1 mol/L of LiOH and 0.1 mol/L of HAc solution to the electrolyte.
  • the battery was charged and discharged at a rate of 0.5 C at a voltage range of 1.5-2.1 V at room temperature.
  • Fig. 9 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 8. As can be seen from the figure, the battery discharge cycle has almost no attenuation at 30 discharge capacities, indicating that the battery provided by the present invention has good charge and discharge stability.
  • LiMn 2 0 4 was used as the positive electrode active material, and the positive electrode active material, super-p carbon black, and binder CMC-SBR were uniformly mixed in a weight ratio of 90.5:1:2.5:6, and NMP was used as a dispersing agent to prepare a positive electrode slurry.
  • the positive electrode slurry was uniformly coated on a positive electrode current collector stainless steel mesh having a thickness of 0.1 mm by a slurry drawing method, and the surface density of the positive electrode active material was 1500 g/m 2 , followed by drying and pressing to obtain a positive electrode having a coating thickness of 0.74 mm.
  • the negative electrode was a metal zinc foil having a thickness of 50 ⁇ m.
  • the diaphragm is glass fiber (AGM).
  • the electrolytic solution was an aqueous solution containing 2 mol/L of zinc sulfate and 0.5 mol/L of lithium sulfate, and the pH of the electrolyte was about 3.5.
  • the battery was charged and discharged at room temperature with a voltage range of 1.4-2. IV, and the charging rate was 0.2C.
  • the battery performance at different discharge rates was investigated.
  • the batteries provided in Example 9 were discharged at 0.25 C, 1 C, 2 C and 4 C, respectively, and the battery was discharged at 0.25 C for the first discharge capacity of 115 mAh/g. As the discharge rate increased, the first discharge capacity of the battery slightly decreased.

Abstract

Provided is a battery, comprising a positive electrode, a negative electrode and an electrolytic solution. The positive electrode comprises a positive electrode current collector and a coating formed on the positive electrode current collector, the coating at least comprises a positive electrode active substance which participates in the positive electrode reaction, and the positive electrode active substance can reversibly de-intercalate an inserted ion; the negative electrode at least comprises a negative electrode current collector; and the electrolyte solution comprises a solvent and an electrolyte, wherein the solvent is selected from water or alcohol, and the electrolyte can at least ionize an active ion which performs reduction-deposition and oxidation-dissolving in the negative electrode in the charging or discharging process. The areal density range of the positive electrode active substance in the coating is 100-3000 g/m2. The battery provided in the present invention has an excellent electrochemical performance, a higher energy density, and a good cycle performance. The operation of the battery is secure, and the production cost thereof is low.

Description

电池 技术领域  Battery technology
本发明属于电化学储能领域， 具体涉及一种电池。  The invention belongs to the field of electrochemical energy storage, and particularly relates to a battery.
背景技术 Background technique
近年来， 随着科技的发展， 对能源尤其是可再生绿色能源的需求越来越 突出， 电池作为能量的储存和转换装置正发挥着不可替代的作用。 在诸多种 类是电池中， 锂二次电池与传统的镍氢、 镍镉二次电池相比具有很多优点， 比如能量密度大， 重量轻， 可应用于笔记本电脑等便携式电子产品中； 工作 电压高、 自放电低、 循环寿命长、 无记忆效应， 可多次充放； 工作温度宽， 可在许多极端环境下使用； 安全性能好， 工作时无气体产生； 无环境公害， 有利于环境保护等。  In recent years, with the development of science and technology, the demand for energy, especially renewable green energy, has become more and more prominent. The battery as an energy storage and conversion device is playing an irreplaceable role. Among many types of batteries, lithium secondary batteries have many advantages compared with conventional nickel-hydrogen and nickel-cadmium secondary batteries, such as high energy density and light weight, which can be applied to portable electronic products such as notebook computers; Low self-discharge, long cycle life, no memory effect, can be charged and discharged multiple times; Wide operating temperature, can be used in many extreme environments; Good safety performance, no gas generated during work; No environmental pollution, Conducive to environmental protection, etc. .
然而， 现有的锂二次电池的容量仍旧较小， 仍旧无法满足人们 日常工作 生活的需求。 比如， 笔记本在使用电池供电工作时， 仅仅能够使用约 2个小 时， 多数智能手机待机时间只有 1 到 2天。 如果使用者外出工作时间较长没 有及时为电池充电， 则会给使用者的工作和生活带来不便。  However, the capacity of existing lithium secondary batteries is still small, and still cannot meet the needs of people's daily work and life. For example, when a notebook is running on battery power, it can only be used for about 2 hours, and most smartphones have a standby time of only 1 to 2 days. If the user goes out for a long period of time and does not charge the battery in time, it will cause inconvenience to the user's work and life.
因此， 现有技术实有必要进一步提高。  Therefore, it is necessary to further improve the prior art.
发明 内容 Invention content
本发明旨在提供一种具有良好电化学性能以及高能量密度的电池。  The present invention is directed to a battery having good electrochemical performance and high energy density.
本发明提供一种电池， 包括正极、 负极和电解液， 所述正极包括正极集 流体和形成于所述正极集流体上的涂层， 所述涂层至少包括参与正极反应的 正极活性物质， 所述正极活性物质能够可逆脱出 -嵌入离子； 所述负极至少包 括负极集流体； 所述电解液包括溶剂和电解质， 所述溶剂选自水或醇， 所述 电解质至少能够电离出在充放电过程中在所述负极发生还原 -沉积和氧化-溶 解的活性离子； 所述涂层中正极活性物质的面密度范围为 1 00-3000g/m2。 The present invention provides a battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising a positive electrode current collector and a coating layer formed on the positive electrode current collector, the coating layer comprising at least a positive electrode active material participating in a positive electrode reaction, The positive electrode active material is capable of reversibly extracting-embeding ions; the negative electrode includes at least a negative electrode current collector; the electrolyte solution includes a solvent and an electrolyte, and the solvent is selected from water or alcohol, and the electrolyte is at least capable of being ionized during charging and discharging. Reactive-deposited and oxidized-dissolved active ions are generated in the negative electrode; the areal density of the positive active material in the coating ranges from 100 to 3000 g/m 2 .
优选的， 所述涂层中正极活性物质的面密度为 300- 1 500g/m2。 Preferably, the surface active density of the positive electrode active material in the coating layer is from 300 to 1 500 g/m 2 .
优选的， 所述涂层的厚度范围为 40- 1000μηι。  Preferably, the thickness of the coating ranges from 40 to 1000 μm.
本发明还提供了一种电池， 包括正极、 负极和电解液， 所述正极包括正 极集流体和形成于所述正极集流体上的涂层， 所述涂层至少包括参与正极反 应的正极活性物质， 所述正极活性物质能够可逆脱出 -嵌入离子； 所述负极至 少包括负极集流体； 所述电解液包括溶剂和电解质， 所述溶剂选自水或醇， 所述电解质至少能够电离出在充放电过程中在所述负极发生还原-沉积和氧 化 -溶解的活性离子； 所述涂层的厚度范围为 40- 1000μηι。 The present invention also provides a battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising a positive electrode current collector and a coating layer formed on the positive electrode current collector, the coating layer comprising at least a positive electrode active material participating in a positive electrode reaction The positive active material is capable of reversibly extracting-embeding ions; the negative electrode includes at least a negative current collector; the electrolyte includes a solvent and an electrolyte, and the solvent is selected from water or alcohol. The electrolyte is capable of at least ionizing reactive ions that undergo reduction-deposition and oxidation-dissolution at the negative electrode during charge and discharge; the thickness of the coating ranges from 40 to 1000 μm.
优选的， 所述正极活性物质占所述涂层的比重范围为 60-99%。  Preferably, the positive electrode active material accounts for 60-99% of the specific gravity of the coating layer.
优选的， 所述涂层还包括导电剂， 所述导电剂占所述涂层的比重范围为 Preferably, the coating further includes a conductive agent, and the conductive agent accounts for a specific gravity range of the coating.
0.5-30%。 0.5-30%.
优选的， 所述涂层还包括粘结剂， 所述粘结剂占所述涂层的比重范围为 0.5- 10%。  Preferably, the coating further comprises a binder, the binder having a specific gravity ranging from 0.5 to 10%.
优选的， 所述正极集流体的厚度范围为 5- 100μηι。  Preferably, the positive electrode current collector has a thickness ranging from 5 to 100 μm.
优选的， 所述正极集流体的材料选自碳基材料、 金属或合金中的一种， 其中， 所述碳基材料选自玻璃碳、 石墨箔、 泡沫碳、 碳毡、 碳纤维中的一种； 其中， 所述金属选自 Al、 Fe、 Cu、 Pb、 Ti、 Cr、 Mo、 Co、 Ag或经过钝化处 理的上述金属中的一种； 其中， 所述合金选自不锈钢、 A1合金、 Ni合金、 Ti 合金、 Cu合金、 Co合金、 Ti-Pt合金、 Pt-Rh合金或经过钝化处理的上述合 金中的一种。  Preferably, the material of the cathode current collector is selected from one of a carbon-based material, a metal or an alloy, wherein the carbon-based material is selected from the group consisting of glassy carbon, graphite foil, foamed carbon, carbon felt, and carbon fiber. Wherein the metal is selected from the group consisting of Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or a passivated one of the above metals; wherein the alloy is selected from the group consisting of stainless steel, Al alloy, One of a Ni alloy, a Ti alloy, a Cu alloy, a Co alloy, a Ti-Pt alloy, a Pt-Rh alloy, or a passivated alloy.
优选的，所述正极集流体为不锈钢网，所述不锈钢网的规格选自 100 目 、 1 10 目 、 120 目 、 150 目 、 160 目 、 180 目 、 200 目 、 250 目 、 270 目 300 目 。  Preferably, the cathode current collector is a stainless steel mesh, and the size of the stainless steel mesh is selected from the group consisting of 100 mesh, 10 mesh, 120 mesh, 150 mesh, 160 mesh, 180 mesh, 200 mesh, 250 mesh, and 270 mesh 300 mesh.
优选的， 所述正极集流体为经过钝化处理的不锈钢网。  Preferably, the cathode current collector is a passivated stainless steel mesh.
本发明提供的电池，涂层中正极活性物质的面密度设置为 100-3000g/m2 , 电池具有优异的电化学性能、 较高的能量密度以及良好的循环性能， 电池操 作安全， 生产成本低， 适合作为大型储能领域的储能体系以及铅酸电池的替 代品。 The battery provided by the invention has the surface density of the positive active material in the coating set to 100-3000 g/m 2 , and the battery has excellent electrochemical performance, high energy density and good cycle performance, safe battery operation and low production cost. It is suitable as an energy storage system for large-scale energy storage and as an alternative to lead-acid batteries.
附图说明 DRAWINGS
图 1是实施例 1提供的电池的放电容量与循环次数的关系曲线图； 图 2是实施例 2提供的电池的放电容量与循环次数的关系曲线图； 图 3是实施例 3提供的电池的放电容量与循环次数的关系曲线图； 图 4是实施例 3提供的电池的库伦效率与循环次数的关系曲线图； 图 5是实施例 4提供的电池的放电容量与循环次数的关系曲线图； 图 6是实施例 5提供的电池的放电容量与循环次数的关系曲线图； 图 7是实施例 5提供的电池的库伦效率与循环次数的关系曲线图； 图 8是实施例 7提供的电池的放电容量与循环次数的关系曲线图； 图 9是实施例 8提供的电池的放电容量与循环次数的关系曲线图。 具体实施方式 1 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 1. FIG. 2 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 2. FIG. FIG. 4 is a graph showing the relationship between the coulombic efficiency and the number of cycles of the battery provided in Example 3; FIG. 5 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 4; 6 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 5; FIG. 7 is a graph showing the relationship between the coulombic efficiency and the number of cycles of the battery provided in Example 5; FIG. 9 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 8. FIG. detailed description
一种电池， 电池可以应用于如手机、 笔记本电脑等便携式电子产品， 电 动汽车， 电动工具等。  A battery that can be applied to portable electronic products such as mobile phones and notebook computers, electric cars, electric tools, and the like.
一种电池， 包括正极、 负极和电解液， 正极包括正极集流体和形成于正 极集流体上的涂层， 涂层至少包括参与正极反应的正极活性物质。  A battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising a positive electrode current collector and a coating formed on the positive electrode current collector, the coating layer comprising at least a positive electrode active material participating in the positive electrode reaction.
正极活性物质占涂层的重量百分比范围为 60-99%, 涂层中正极活性物质 的面密度范围为 100-3000g/m2, 优选的， 涂层中正极活性物质的面密度范围 为 300-1500g/m2, 涂层厚度范围为 40-1000μηι。 The positive electrode active material accounts for 60-99% by weight of the coating layer, and the surface density of the positive electrode active material in the coating ranges from 100 to 3000 g/m 2 . Preferably, the surface density of the positive electrode active material in the coating ranges from 300 to 300- 1500 g/m 2 , coating thickness ranging from 40 to 1000 μm.
本发明还提供了一种电池， 包括正极、 负极和电解液， 正极包括正极集 流体和形成于正极集流体上的涂层， 涂层至少包括参与正极反应的正极活性 物质， 涂层厚度范围为 40-1000μηι。  The invention also provides a battery comprising a positive electrode, a negative electrode and an electrolyte, the positive electrode comprising a positive electrode current collector and a coating formed on the positive electrode current collector, the coating layer comprising at least a positive electrode active material participating in the positive electrode reaction, and the coating thickness ranges from 40-1000μηι.
在制备涂层的过程中， 一般涉及对涂覆干燥成型的正极进行压制处理， 压制处理后的涂层厚度范围为 40-1000μηι, 涂层没有出现干裂或掉粉现象， 依照该设计制造的正极具有优良的电化学性能。  In the process of preparing the coating, generally, the coating dry-formed positive electrode is subjected to pressing treatment, and the thickness of the coating after the pressing treatment ranges from 40 to 1000 μm, and the coating has no dry cracking or powder falling phenomenon, and the positive electrode is manufactured according to the design. Has excellent electrochemical properties.
具体的， 正极活性物质能够可逆脱出 -嵌入离子。 优选的， 正极活性物质 能够可逆脱出-嵌入锂离子、 钠离子或镁离子。  Specifically, the positive electrode active material is capable of reversibly extracting - intercalating ions. Preferably, the positive electrode active material is capable of reversibly extracting - intercalating lithium ions, sodium ions or magnesium ions.
在具体的实施方式中， 正极活性物质是符合通式 Li1+xMnyMzOk的能够可 逆脱出-嵌入锂离子的尖晶石结构的化合物， 其中， -l≤ x≤0.5, 1< y <2.5, 0< z <0.5, 3< k <6, M选自 Na、 Li、 Co、 Mg、 Ti、 Cr、 V、 Zn、 Zr、 Si、 Al t 的至少一种。 优选的， 正极活性物质含有 LiMn204。 更优选的， 正极活性物 质含有经过掺杂或包覆改性的 LiMn204。 In a specific embodiment, the positive electrode active material is a compound capable of reversibly deintercalating-intercalating lithium ion-doped spinel structure conforming to the general formula Li 1+x Mn y M z O k , wherein -l≤x≤0.5, 1 < y < 2.5, 0 < z < 0.5, 3 < k < 6, M is at least one selected from the group consisting of Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, and Al t . Preferably, the positive electrode active material contains LiMn 2 0 4 . More preferably, the positive active material contains LiMn 2 0 4 which is doped or coated modified.
在具体的实施方式中，正极活性物质是符合通式 Li l+xMyM'zM"c02 + n的能 够可逆脱出-嵌入锂离子的层状结构的化合物， 其中， -l< x≤0.5, 0< y <1, 0< z <1 , 0< c <1 , -0.2< n <0.2, M, Μ', Μ"分别选自 Ni、 Mn、 Co、 Mg、 Ti、 Cr、 V、 Zn、 Zr、 Si或 Al的中至少一种。 优选的， 正极活性物质含有 LiCo02。 In a specific embodiment, the positive active material is a compound capable of reversibly deintercalating-intercalating lithium ion in a layered structure conforming to the general formula Li l+ x M y M' z M" c 02 + n, wherein -l < x ≤ 0.5, 0< y <1, 0< z <1 , 0< c <1 , -0.2< n <0.2, M, Μ', Μ" are respectively selected from Ni, Mn, Co, Mg, Ti, Cr, V At least one of Zn, Zr, Si or Al. Preferably, the positive electrode active material contains LiCo0 2 .
在具体的实施方式中， 正极活性物质是符合通式 LixM^yM'y(X04)n的能 够可逆脱出-嵌入锂离子的橄榄石结构的化合物， 其中， 0< x≤2, 0< y <0.6, 1< n <1.5, M选自 Fe、 Mn、 V或 Co, M'选自 Mg、 Ti、 Cr、 V或 Al的中至 少一种， X选自 S、 P或 Si中的至少一种。优选的，正极活性物质含有 LiFeP04。 In a specific embodiment, the positive active material is a compound capable of reversibly deintercalating-intercalating lithium ion olivine structure according to the general formula Li x M^ y M' y (X0 4 ) n , wherein 0< x≤2, 0< y <0.6, 1< n <1.5, M is selected from Fe, Mn, V or Co, and M' is at least one selected from the group consisting of Mg, Ti, Cr, V or Al, and X is selected from S, P or Si. At least one of them. Preferably, the positive electrode active material contains LiFePO 4 .
目前锂电池工业中， 几乎所有正极活性物质都会经过掺杂、 包覆等改性 处理。 但掺杂， 包覆改性等手段造成材料的化学通式表达复杂， 如 LiMn204 已经 不 能够代表 目 前广 泛使用 的 "锰酸锂 "的通式 ， 而应该 以 通式 Li1 +xMnyMzOk为准， 广泛地包括经过各种改性的 LiMn204正极活性物质。 同 样的， LiFeP04以及 LiCo02也应该广泛地理解为包括经过各种掺杂、 包覆等 改性的， 通式分别符合 LixM1 -yM'y(X04)n和 Li1 +xMyM'zM"c02+n的正极活性物 质。 At present, in the lithium battery industry, almost all positive active materials are subjected to modification treatment such as doping and coating. However, doping, coating modification and other means cause the chemical formula of the material to be complex, such as LiMn 2 0 4 It has not been able to represent the general formula of "manganese manganate" which is widely used at present, but should be based on the general formula Li 1 + x Mn y M z O k , and broadly include various modified LiMn 2 0 4 positive electrode activities. substance. Similarly, LiFeP0 4 and LiCo0 2 should also be broadly understood to include modifications through various doping, cladding, etc., which are in accordance with Li x M 1 -y M' y (X0 4 ) n and Li 1 + , respectively. x M y M' z M" c 0 2+n positive electrode active material.
正极活性物质为锂离子脱出 -嵌入化合物时， 可以选用如 LiMn204、 LiFeP04、 LiCo02、 LiMxP04、 LiMxSiOy (其中 M 为一种变价金属）等化合物。 此外， 可脱出-嵌入钠离子的化合物 NaVP04F , 可脱出-嵌入镁离子的化合物 MgMxOy (其中 M为一种金属， 0.5< X <3 , 2< y <6)以及具有类似功能， 能够 脱出-嵌入离子或官能团的化合物都可以作为本发明电池的正极活性物质， 因 此， 本发明并不局限于锂离子电池。 When the positive electrode active material is a lithium ion elution-embedded compound, a compound such as LiMn 2 0 4 , LiFeP0 4 , LiCo0 2 , LiM x P0 4 , LiM x SiO y (wherein M is a variable metal) may be used. In addition, the compound NaVP0 4 F which can be eluted-inserted with sodium ions can be eluted-embedded into the magnesium ion compound MgM x O y (where M is a metal, 0.5< X <3, 2< y <6) and has similar functions. A compound capable of deintercalating-embedding an ion or a functional group can be used as a positive electrode active material of the battery of the present invention, and therefore, the present invention is not limited to a lithium ion battery.
涂层还包括导电剂， 导电剂主要起到提高涂层的导电子能力， 导电剂占 涂层的重量百分比范围为 0.5 -30%。导电剂包括选自导电聚合物、碳纳米管、 活性碳、 石墨烯、 碳黑、 碳纤维中的至少一种。 碳黑包括但不仅限于乙炔黑、 科琴碳黑（Ketjen black , KB)以及 super-p碳黑。  The coating further includes a conductive agent, and the conductive agent mainly serves to improve the conductivity of the coating, and the conductive agent accounts for 0.5-30% by weight of the coating. The conductive agent includes at least one selected from the group consisting of a conductive polymer, carbon nanotubes, activated carbon, graphene, carbon black, and carbon fibers. Carbon black includes, but is not limited to, acetylene black, Ketjen black (KB), and super-p carbon black.
涂层还包括粘结剂， 粘结剂主要是将活性材料粘附在集流体上的高分子 化合物， 增强活性材料与导电剂以及活性材料与集流体之间的电子接触， 更 好地稳定正极的性能。 粘结剂 占涂层的重量百分比范围为 0.5- 10%。 粘结剂 选自聚四氟乙烯（PTFE)、 聚偏氟乙烯（PVDF)、 羧甲基纤维素钠（CMC)、 羧甲 基纤维素钠衍生物（CMC derivation) , 丁苯橡胶（SBR)、 丁苯橡胶衍生物（SBR derivation)中的至少一种。丁苯橡胶衍生物如通过化学修饰获得的具有亲水性 的丁苯橡胶（PSBR100)。  The coating further comprises a binder, the binder is mainly a polymer compound for adhering the active material to the current collector, enhancing the electronic contact between the active material and the conductive agent and the active material and the current collector, thereby better stabilizing the positive electrode. Performance. The binder accounts for 0.5 to 10% by weight of the coating. The binder is selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose derivative (CMC derivation), and styrene butadiene rubber (SBR). At least one of a styrene-butadiene rubber derivative (SBR derivation). A styrene-butadiene rubber derivative such as a hydrophilic styrene-butadiene rubber (PSBR100) obtained by chemical modification.
正极集流体主要是作为传导和收集电子的载体， 正极集流体的材料包括 碳基材料、 金属或合金中的一种。  The positive electrode current collector is mainly used as a carrier for conducting and collecting electrons, and the material of the positive electrode current collector includes one of a carbon-based material, a metal or an alloy.
碳基材料选自玻璃碳、 石墨箔、 泡沫碳、 碳毡、 碳纤维中的一种。 在一 个具体的实施方式中， 正极集流体为石墨， 如商业化的石墨压制的箔， 其中 石墨所占的重量比例范围为 90- 100%。  The carbon-based material is selected from the group consisting of glassy carbon, graphite foil, foamed carbon, carbon felt, and carbon fiber. In a specific embodiment, the positive current collector is graphite, such as a commercial graphite pressed foil, wherein the weight ratio of graphite ranges from 90 to 100%.
金属为金属网或金属箔， 金属包括 Al、 Fe、 Cu、 Pb、 Ti、 Cr、 Mo、 Co、 Ag或经过钝化处理的上述金属中的一种。 在一个具体的实施方式中， 正极集 流体选自钝化处理的铝箔。  The metal is a metal mesh or a metal foil, and the metal includes one of Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the above-mentioned metal which has been passivated. In a specific embodiment, the positive current collector is selected from the group consisting of passivated aluminum foil.
将金属进行钝化处理的主要目 的是使金属的表面形成一层钝化膜， 从而 在电池充放电过程中， 能起到稳定的收集和传导电子的作用， 而不会参与正 极反应， 保证电池性能。 The main purpose of passivating the metal is to form a passivation film on the surface of the metal. During the charging and discharging process of the battery, it can stably collect and conduct electrons, and does not participate in the positive electrode reaction to ensure battery performance.
合金包括不锈钢、 A1合金、 Ni合金、 Ti合金、 Cu合金、 Co合金、 Ti-Pt 合金、 Pt- h合金或经过钝化处理的上述金属中的一种。  The alloy includes one of stainless steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-h alloy or passivated.
不锈钢包括不锈钢网、 不锈钢箔， 不锈钢的型号包括但不仅限于不锈钢 304或者不锈钢 3 16或者不锈钢 3 16L中的一种。 在具体实施方式中， 正极集 流体采用型号为 304的不锈钢箔。 若正极集流体采用不锈钢网， 则不锈钢网 的规格范围选自 100 目 、 1 10 目 、 120 目 、 150 目 、 160 目 、 1 80 目 、 200 目 、 250 目 、 270 目或 300 目 ， 较佳的不锈钢网的规格为 150 目 ， 正极活性物质能 够稳定的涂覆在正极集流体表面， 有利于正极反应的进行。  Stainless steel includes stainless steel mesh, stainless steel foil, and stainless steel models include, but are not limited to, stainless steel 304 or stainless steel 3 16 or stainless steel 3 16L. In a specific embodiment, the positive current collector is a stainless steel foil of the type 304. If the cathode current collector is made of stainless steel mesh, the specification range of the stainless steel mesh is selected from 100 mesh, 10 mesh, 120 mesh, 150 mesh, 160 mesh, 180 mesh, 200 mesh, 250 mesh, 270 mesh or 300 mesh, preferably The stainless steel mesh has a size of 150 mesh, and the positive electrode active material can be stably coated on the surface of the positive electrode current collector to facilitate the progress of the positive electrode reaction.
在正极集流体上涂覆涂层的过程中， 可以在正极集流体的两侧均涂覆涂 层， 也可以仅在一侧涂覆涂层， 在具体一个实施方式中， 正极集流体为不锈 钢网或箔， 在不锈钢网或不锈钢箔的两侧均涂覆涂层， 而不锈钢网或不锈钢 箔的任一侧为单层涂层。 单层涂层的厚度范围为 40- 1000μηι。  In the process of coating the coating on the positive current collector, the coating may be applied on both sides of the positive current collector, or the coating may be applied on only one side. In a specific embodiment, the positive current collector is stainless steel. Mesh or foil, coated on both sides of a stainless steel mesh or stainless steel foil, and either side of the stainless steel mesh or stainless steel foil is a single layer coating. The thickness of the single layer coating ranges from 40 to 1000 μm.
同样的， 将不锈钢进行钝化处理也是使其能够稳定的起到收集和传导电 子的作用， 而不会参与正极反应， 保证电池性能。 在具体实施方式中， 钝化 不锈钢的具体过程为： 在 50 °C下， 将不锈钢置入 20%的硝酸中半小时， 使不 锈钢表面形成一层钝化膜。 钝化后的不锈钢作为集流体使用。  Similarly, the passivation treatment of stainless steel also enables it to stably collect and conduct electrons without participating in the positive electrode reaction to ensure battery performance. In a specific embodiment, the specific process of passivating the stainless steel is: placing the stainless steel in 20% nitric acid at 50 ° C for half an hour to form a passivation film on the surface of the stainless steel. The passivated stainless steel is used as a current collector.
正极集流体的厚度对正极的电化学性能有一定影响， 正极集流体的厚度 太薄， 会影响正极集流体的机械强度； 正极集流体的厚度太厚， 会增加正极 的重量， 从而影响正极的能量密度， 在本发明中， 正极集流体的厚度为 5 - 100μηι , 在优选的实施方式中， 正极集流体的厚度为 50μηι。  The thickness of the positive current collector has a certain influence on the electrochemical performance of the positive electrode. The thickness of the positive current collector is too thin, which will affect the mechanical strength of the positive current collector. The thickness of the positive current collector is too thick, which will increase the weight of the positive electrode and affect the positive electrode. Energy density, in the present invention, the thickness of the positive electrode current collector is 5 - 100 μηι, and in a preferred embodiment, the thickness of the positive electrode current collector is 50 μηι.
负极至少包括负极集流体， 在一个负极的实施方式中， 负极仅包括负极 集流体。 负极集流体仅作为电子传导和收集的载体， 不参与电化学反应。 负 极集流体的材料选自金属 Ni、 Cu、 Ag、 Pb、 Sn、 Fe、 Al或经过钝化处理的 上述金属中的至少一种， 或者碳基材料， 或者不锈钢。 其中， 碳基材料包括 石墨材料， 比如商业化的石墨压制的箔， 其中石墨所占的重量比例范围为 90- 100%。 不锈钢材料包括但不仅限于不锈钢 304 或者不锈钢 3 16 或者不锈 钢 3 16L。  The negative electrode includes at least a negative current collector, and in one negative electrode embodiment, the negative electrode includes only the negative current collector. The anode current collector acts only as a carrier for electron conduction and collection and does not participate in the electrochemical reaction. The material of the negative current collector is selected from at least one of the metals Ni, Cu, Ag, Pb, Sn, Fe, Al or the passivated metal, or a carbon-based material, or stainless steel. Among them, carbon-based materials include graphite materials, such as commercial graphite-pressed foils, in which graphite accounts for 90-100% by weight. Stainless steel materials include, but are not limited to, stainless steel 304 or stainless steel 3 16 or stainless steel 3 16L.
负极集流体还可以选自含有析氢电位高的镀 /涂层的金属， 从而降低负极 副反应的发生。 镀 /涂层选自含有 C、 Sn、 In , Ag、 Pb、 Co、 Zn 的单质， 合 金， 或者氧化物中至少一种。 镀 /涂层的厚度范围为 l - 1000nm。 例如： 在铜 的负极集流体表面镀上铅或银， 或者以涂覆的形式覆盖一层碳。 The anode current collector may also be selected from a metal containing a plating/coating having a high hydrogen evolution potential, thereby reducing the occurrence of negative side reactions. The plating/coating is selected from the group consisting of C, Sn, In, Ag, Pb, Co, and Zn. Gold, or at least one of oxides. The thickness of the plating/coating ranges from 1 to 1000 nm. For example: The surface of the negative current collector of copper is plated with lead or silver, or coated with a layer of carbon.
电解液包括溶剂和至少一种电解质， 溶剂包括水溶液或者醇溶液中的至 少一种， 醇溶液包括但不仅限于乙醇或甲醇。 电解质能够电离出在充放电过 程中在负极发生还原 -沉积和氧化 -溶解的活性离子。  The electrolyte includes a solvent and at least one electrolyte, and the solvent includes at least one of an aqueous solution or an alcohol solution including, but not limited to, ethanol or methanol. The electrolyte is capable of ionizing reactive ions which undergo reduction-deposition and oxidation-dissolution at the negative electrode during charge and discharge.
活性离子包括金属离子， 金属选自 Zn、 Fe、 Cr、 Cu、 Mn、 Ni中的至少 一种。 在优选的实施方式中， 活性离子为 Zn2+。 活性离子的浓度范围为 0.5 - 1 5mol/L。 The living ions include metal ions selected from at least one of Zn, Fe, Cr, Cu, Mn, and Ni. In a preferred embodiment, the reactive ion is Zn 2+ . The concentration of the active ions ranges from 0.5 to 15 mol/L.
金属离子以氯酸盐、 4 酸盐、 硝酸盐、 醋酸盐、 甲酸盐、 磷酸盐中一种 或几种形式存在于电解液中。  The metal ion is present in the electrolyte in one or more of a chlorate, a tetra-acid salt, a nitrate salt, an acetate salt, a formate salt, or a phosphate.
正极集流体为钝化处理的不锈钢时， 优选的， 金属离子以硫酸盐或硝酸 盐或醋酸盐的形式存在于电解液中； 正极集流体为钝化处理的金属铝时， 优 选的， 金属离子以硫酸盐或醋酸盐的形式存在于电解液中。  When the cathode current collector is passivated stainless steel, preferably, the metal ions are present in the electrolyte in the form of sulfate or nitrate or acetate; when the cathode current collector is passivated metal aluminum, preferably, metal The ions are present in the electrolyte in the form of sulfate or acetate.
更优选的， 电解液中还包括一种电解质， 这种电解质可以电离出对应在 正极能够发生可逆脱出-嵌入的离子。  More preferably, the electrolyte further includes an electrolyte which can be ionized to correspond to ions capable of reversible elution-embedding at the positive electrode.
电解液中含有能够可逆脱出 -嵌入的离子， 从而可以提高正极活性物质与 电解液中离子交换速度。 具体的， 正极活性物质为能够可逆脱出 -嵌入锂离子 的化合物， 电解质中对应的还包括锂离子。 可逆脱出 -嵌入的离子包括锂离子 或钠 离 子或镁离 子， 可逆脱出 -嵌入的 离 子在电解液中 的浓度范围 为 0. 1 - 1 0mol/L。 在具体实施方式中， 电解液包含锂， 锌的硝酸、硫酸或醋酸盐。  The electrolyte contains reversible elution-embedded ions, so that the ion exchange rate between the positive electrode active material and the electrolyte can be increased. Specifically, the positive electrode active material is a compound capable of reversibly deintercalating-intercalating lithium ions, and the electrolyte further includes lithium ions. Reversible extraction - The embedded ions include lithium ions or sodium ions or magnesium ions, and the reversible deionization-embedded ions have a concentration in the electrolyte ranging from 0.1 to 1 mol/L. In a specific embodiment, the electrolyte comprises lithium, zinc, nitric acid, sulfuric acid or acetate.
为了保证电池容量， 电解液中的活性离子的浓度必须达到一定范围， 当 电解液过碱时， 会影响电解液中活性离子的溶解度； 当电解液过酸时， 则会 出现电极材料腐蚀和充放电过程中质子共嵌入等问题， 因此， 电解液的 pH 值范围为 3 -7。  In order to ensure the battery capacity, the concentration of active ions in the electrolyte must reach a certain range. When the electrolyte is over-alkali, it will affect the solubility of the active ions in the electrolyte; when the electrolyte is too acidic, the electrode material will corrode and charge. Problems such as proton embedding during discharge, therefore, the pH of the electrolyte ranges from 3 -7.
电池的充放电原理为： 充电时， 正极活性物质中脱出可逆脱出-嵌入的离 子， 同时伴随正极活性物质内变价金属被氧化， 并放出电子； 电子经由外电 路到达电池负极， 同时电解液中的活性离子在负极得到电子被还原， 并沉积 在负极。 放电过程为充电的逆过程。  The charging and discharging principle of the battery is as follows: During charging, the reversible elution-embedded ions are removed from the positive active material, and at the same time, the metal in the positive active material is oxidized and the electrons are released; the electrons reach the negative electrode of the battery through the external circuit, and at the same time in the electrolyte The active ions are reduced at the negative electrode and deposited on the negative electrode. The discharge process is the reverse process of charging.
电池使用水溶液电解液， 不存在有机电解液易燃等安全隐患， 并且水系 电解液相对于有机电解液具有更高的离子导电率， 减小了电池极化的影响， 因此，本发明提供的电池，涂层中正极活性物质面密度范围为 1 00-3000g/m2 , 使得电池可以具有非常大的比容量和能量， 同时又具有非常优良的电化学性 能。 The battery uses an aqueous solution electrolyte, there is no safety hazard such as flammability of the organic electrolyte, and the aqueous electrolyte has higher ionic conductivity than the organic electrolyte, which reduces the influence of battery polarization. Therefore, the battery provided by the present invention The surface active density of the positive active material in the coating ranges from 100 to 3000 g/m 2 . This allows the battery to have a very large specific capacity and energy while having very excellent electrochemical performance.
在另一个负极的实施方式中， 负极仅包括负极集流体， 同时负极集流体 的选材与电解液中活性离子的对应，即负极集流体的材料为活性离子的单质， 如电解液中活性离子为 Zn2+, 负极对应为金属 Zn。 此时， 负极不仅是作为活 性离子的沉积载体， 同时也可以参与电池反应。 In another embodiment of the negative electrode, the negative electrode includes only the negative current collector, and the material of the negative current collector corresponds to the active ion in the electrolyte, that is, the material of the negative current collector is a simple substance of the active ion, such as the active ion in the electrolyte. Zn 2+ , the negative electrode corresponds to metal Zn. At this time, the negative electrode is not only a deposition carrier as a living ion, but also participates in a battery reaction.
在另一个负极的实施方式中， 负极包括负极集流体和负极活性物质， 负 极活性物质的选材与电解液中活性离子的对应， 即负极活性物质的材料为活 性离子的单质， 如电解液中活性离子为 Zn2+, 负极活性物质对应为金属 Zn。 In another embodiment of the negative electrode, the negative electrode includes a negative electrode current collector and a negative electrode active material, and the material of the negative electrode active material corresponds to the active ion in the electrolyte, that is, the material of the negative electrode active material is a simple substance of the active ion, such as an active substance in the electrolyte. The ion is Zn 2+ , and the negative electrode active material corresponds to metal Zn.
本发明提供的电池在制造过程中可设置隔膜， 隔膜包括有机或无机的多 孔材料， 隔膜的孔隙率范围为 20-95%, 孔径范围为 0.001-100μηι。  The battery provided by the present invention may be provided with a separator during the manufacturing process, and the separator comprises an organic or inorganic porous material having a porosity ranging from 20 to 95% and a pore diameter ranging from 0.001 to 100 μm.
本发明提供的电池，涂层中正极活性物质的面密度范围为 100-3000g/m2, 优选的， 正极活性物质的面密度为 300-1500g/m2, 使得应用所述涂层的电池 具有良好的电化学性能， 并且电池在充放电过程中表现了优异的循环性能， 因此， 本发明的电池在低电压如铅蓄电池、 碱性锌锰电池等应用领域有很大 的应用潜力。 The battery provided by the present invention has an areal density of the positive electrode active material in the coating ranging from 100 to 3000 g/m 2 , and preferably, the areal active material has an areal density of 300 to 1500 g/m 2 , so that the battery to which the coating is applied has Good electrochemical performance, and the battery exhibits excellent cycle performance during charge and discharge. Therefore, the battery of the present invention has great application potential in low voltage applications such as lead storage batteries and alkaline zinc manganese batteries.
下面通过具体实施例来进一步阐述本发明的方案。  The solution of the present invention is further illustrated by the following specific examples.
实施例 1  Example 1
一种电池， 电池正极的集流体采用规格为 304 的不锈钢棒， 正极涂层的 活性材料采用 LiMn204, LiMn204的面密度为 500g/m2, 负极采用规格为 304 的不锈钢棒，电解液为 lmol/L的醋酸锂和 1.5mol/L的醋酸锌的混合水溶液。 A battery, the current collector of the battery is made of a stainless steel rod of size 304, the active material of the positive electrode coating is LiMn 2 0 4 , the surface density of LiMn 2 0 4 is 500 g/m 2 , and the negative electrode is made of stainless steel rod of size 304. The electrolytic solution was a mixed aqueous solution of 1 mol/L of lithium acetate and 1.5 mol/L of zinc acetate.
对电池进行充放电测试， 电压范围为 1.4-2. IV, 充放电倍率为 1C。  Charge and discharge test the battery, the voltage range is 1.4-2. IV, charge and discharge rate is 1C.
图 1 为电池放电容量与循环次数的关系图， 从图中可以看出， 电池初始 放电容量为 5mAh, 基于正极材料的比容量为 100mAh/g, 经过 200次充放电 之后， 容量仍保持在 90%以上， 具有非常高的容量保持率。  Figure 1 shows the relationship between the discharge capacity of the battery and the number of cycles. It can be seen from the figure that the initial discharge capacity of the battery is 5 mAh, and the specific capacity based on the positive electrode material is 100 mAh/g. After 200 charge and discharge, the capacity remains at 90. Above %, has a very high capacity retention rate.
实施例 2  Example 2
一种电池， 电池正极的集流体采用规格为 304的不锈钢棒， 正极涂层的活 性材料采用 LiMn204, LiMn204的面密度为 300g/m2, 负极采用规格为 304的 不锈钢棒， 电解液为 3mol/L的醋酸锂和 1.5mol/L的醋酸锌的混合水溶液。 A battery, the current collector of the battery is made of stainless steel rod of size 304, the active material of the positive electrode coating layer is LiMn 2 0 4 , the surface density of LiMn 2 0 4 is 300 g/m 2 , and the negative electrode is made of stainless steel rod of specification 304. The electrolytic solution was a mixed aqueous solution of 3 mol/L of lithium acetate and 1.5 mol/L of zinc acetate.
对电池进行充放电测试， 电压范围为 1.4-2. IV, 充放电倍率为 1C。  Charge and discharge test the battery, the voltage range is 1.4-2. IV, charge and discharge rate is 1C.
图 1为电池放电容量与循环次数的关系图， 从图中可以看出， 电池初始放 电容量为 3mAh, 基于正极材料的比容量为 100mAh/g, 并且电池循环 160周后 的容量效率仍有 80%以上， 结果表明该电池具有优异的放电性能和循环性能。 Figure 1 is a diagram showing the relationship between the discharge capacity of the battery and the number of cycles. As can be seen from the figure, the battery is initially placed. The capacity is 3 mAh, the specific capacity based on the positive electrode material is 100 mAh/g, and the capacity efficiency after the battery is cycled for 160 weeks is still more than 80%. The results show that the battery has excellent discharge performance and cycle performance.
实施例 3  Example 3
以 LiL05M .89Coo.03Alo.03O4为正极活性物质， 将正极活性物质、 粘结剂 P VDF、 super-p碳黑按照 83： 10: 7的重量比例混合并且溶解在 N-甲基吡咯 烷酮（NMP)中制得正极浆料， 正极集流体为厚度 lmm的石墨板， 将正极浆料 均匀涂覆于正极集流体上， 正极材料中正极活性物质的面密度为 170g/m2, 涂层厚度为 40um, 在空气中 110°C下干燥 24 小时制成正极。 电池负极集流 体为不锈钢杆。 电解液为含有浓度为 4mol/L氯化锌和 3mol/L氯化锂的去离 子水溶液，通过往电解液中滴定 O.lmol/L氢氧化锂将电解液的 pH值调为 4。 隔膜为玻璃毡布。 将正极、 负极组装成电池， 中间以隔膜隔开， 注入电解液。 待电池组装好之后静置 12小时随后开始以 4C倍率充电和放电。 充放电电压 区间为 1.5-2. IV。 LiL05M .89Coo.03Alo.03O4 was used as the positive electrode active material, and the positive electrode active material, binder P VDF, super-p carbon black were mixed in a weight ratio of 83:10:7 and dissolved in N-methylpyrrolidone (NMP). A positive electrode slurry is prepared in which a positive electrode current collector is a graphite plate having a thickness of 1 mm, and a positive electrode slurry is uniformly coated on a positive electrode current collector. The surface active density of the positive electrode active material in the positive electrode material is 170 g/m 2 , and the coating thickness is 40 um. It was dried in air at 110 ° C for 24 hours to form a positive electrode. The battery anode current collector is a stainless steel rod. The electrolytic solution was a deionized aqueous solution containing a concentration of 4 mol/L of zinc chloride and 3 mol/L of lithium chloride, and the pH of the electrolytic solution was adjusted to 4 by titrating 0.1 mol/L of lithium hydroxide into the electrolytic solution. The diaphragm is a glass felt cloth. The positive electrode and the negative electrode were assembled into a battery, and the separator was partitioned therebetween to inject an electrolyte solution. After the battery was assembled, it was allowed to stand for 12 hours and then charged and discharged at a 4 C rate. The charge and discharge voltage range is 1.5-2. IV.
图 3是实施例 3提供的电池的放电容量与循环次数的关系曲线， 从图中 可以清晰看出， 电池循环 4000次的放电容量与首次放电容量几乎相等， 电池 不仅循环性能非常稳定， 并且循环寿命长。  3 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 3. As is clear from the figure, the discharge capacity of the battery cycle 4000 times is almost equal to the first discharge capacity, and the battery not only has a very stable cycle performance, but also has a cycle. long life.
图 4是实施例 3提供的电池的库伦效率与循环次数的关系曲线， 从图中 可以看出电池循环 4000次后， 库伦效率仍接近 100%, 表明本发明中的电池 的充放电性能非常稳定。  4 is a graph showing the Coulomb efficiency and the number of cycles of the battery provided in Example 3. It can be seen from the figure that the coulombic efficiency is still close to 100% after the battery cycle 4000 times, indicating that the charge and discharge performance of the battery of the present invention is very stable. .
实施例 4  Example 4
以 LiMn204为正极活性物质，将正极活性物质、粘结剂聚四氟乙烯（PTFE)、 super-p碳黑按照 83:10:7的比例混合并且溶解在 N-甲基吡咯烷酮（NMP)中制 得正极浆料。 正极活性物质的面密度为 800g/m2, 涂层的厚度为 0.5mm。 正 极集流体为厚度 30 μ m的不锈钢网， 不锈钢不经过钝化， 将正极浆料均匀涂 覆于正极集流体上， 在空气中 110°C下干燥 24小时制成正极。 电池负极集流 体为厚度 ΙΟμηι铜箔。 电解液为含有浓度为 lmol/L醋酸锂和 1.5mol/L醋酸锌 的水溶液， 通过往电解液中滴定 0.1mol/L氢氧化锂和 0.1mol/L的 HAc将电 解液的 pH值调为 4。 隔膜为玻璃毡布。 将正极、 负极组装成电池， 中间以隔 膜隔开， 注入电解液。 待电池组装好之后静置 12 小时随后开始以 0.5C倍率 充电和放电。 充放电电压区间为 1.5-2. IV。 Using LiMn 2 0 4 as a positive electrode active material, the positive electrode active material, the binder polytetrafluoroethylene (PTFE), and the super-p carbon black were mixed at a ratio of 83:10:7 and dissolved in N-methylpyrrolidone (NMP). A positive electrode slurry was prepared. The surface active density of the positive electrode active material was 800 g/m 2 , and the thickness of the coating layer was 0.5 mm. The positive electrode current collector was a stainless steel mesh having a thickness of 30 μm, and the stainless steel was not passivated. The positive electrode slurry was uniformly coated on the positive electrode current collector, and dried in air at 110 ° C for 24 hours to prepare a positive electrode. The negative electrode current collector of the battery is a copper foil having a thickness of ΙΟμηι. The electrolyte is an aqueous solution containing a concentration of 1 mol/L lithium acetate and 1.5 mol/L zinc acetate. The pH of the electrolyte is adjusted to 4 by titrating 0.1 mol/L lithium hydroxide and 0.1 mol/L HAc into the electrolyte. . The diaphragm is a glass felt cloth. The positive electrode and the negative electrode were assembled into a battery, and the separator was partitioned therebetween to inject an electrolyte solution. After the battery was assembled, it was allowed to stand for 12 hours and then charged and discharged at a rate of 0.5 C. The charge and discharge voltage range is 1.5-2. IV.
图 5是实施例 4提供的电池的放电容量与循环次数的关系曲线。 从图中可 以清晰看到： 电池首次放电容量为， 循环 250次后的放电容量与首次放电容量 几乎没有差别， 表明电池的循环性能非常稳定， 本发明提供的电池具有优异 的电化学性能。 Fig. 5 is a graph showing the discharge capacity of the battery of Example 4 as a function of the number of cycles. From the picture It is clear that the first discharge capacity of the battery is that the discharge capacity after the cycle of 250 times is almost the same as the first discharge capacity, indicating that the cycle performance of the battery is very stable, and the battery provided by the present invention has excellent electrochemical performance.
实施例 5  Example 5
以 LiMn204 为正极活性物质， 将正极活性物质、 super-p 碳黑、 粘接剂 PVDF按照重量比例 83 : 10: 7混合均匀，以 NMP作为分散剂，制得正极浆料， 均匀涂覆在厚度 80μηι 的正极集流体石墨箔上， 正极活性物的面密度为 300g/m2 , 随后干燥、 压制得到正极。 负极为厚度 50μηι的金属锌箔， 金属锌 既是负极活性物质， 同时还兼做负极集流体。 隔膜为无纺纤维布。 电解液为 含有 3mol/L氯化锂和 4mol/L氯化锌的水溶液，通过向电解液中滴加 0. 1 mol/L 的 LiOH溶液调节电解液的 pH为 4。 室温下， 在电压范围 1 .5-2. 1V以 1 C倍 率对电池进行充放电。 LiMn 2 0 4 is used as a positive electrode active material, and a positive electrode active material, super-p carbon black, and a binder PVDF are uniformly mixed in a weight ratio of 83:10:7, and a positive electrode slurry is prepared by using NMP as a dispersing agent. The positive electrode current collector graphite foil was coated on a thickness of 80 μm, and the surface active density of the positive electrode active material was 300 g/m 2 , followed by drying and pressing to obtain a positive electrode. The negative electrode is a metal zinc foil having a thickness of 50 μm, and the metal zinc is both a negative electrode active material and also serves as a negative electrode current collector. The separator is a non-woven fabric. The electrolytic solution was an aqueous solution containing 3 mol/L of lithium chloride and 4 mol/L of zinc chloride, and the pH of the electrolytic solution was adjusted to 4 by dropwise addition of 0.1 mol/L of LiOH solution to the electrolytic solution. The battery was charged and discharged at a rate of 1 C in a voltage range of 1.5 to 2.1 V at room temperature.
图 6为实施例 5提供的电池的放电容量与循环次数的关系曲线， 电池在 循环 30次后容量略有衰减， 但衰减速率很慢。  Fig. 6 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 5. The battery was slightly attenuated after 30 cycles, but the decay rate was very slow.
图 7为实施例 5提供的电池的库伦效率与循环次数的关系曲线， 电池在 循环 30次后的库伦效率将近 90%。  Figure 7 is a graph showing the Coulomb efficiency versus the number of cycles for the battery provided in Example 5. The coulombic efficiency of the battery after 30 cycles was nearly 90%.
实施例 6  Example 6
以 LiMn204 为正极活性物质， 将正极活性物质、 super-p 碳黑、 粘接剂 CMC-SB 按照重量比例 83 : 10: 7 混合均匀， 以 NMP作为分散剂， 制得正极 浆料， 均勾涂覆在厚度 50μηι 的正极集流体不锈钢箔上， 正极活性物质的面 密度为 700g/m2 , 涂层厚度为 0.4mm , 不锈钢不经过钝化， 随后干燥、 压制 得到正极。 负极为厚度 40μηι 的金属锌箔， 金属锌既是负极活性物质， 同时 还兼做负极集流体。隔膜为玻璃毡布。电解液为含有 l mol/L醋酸锂和 1 .5mol/L 醋酸锌的水溶液， 通过向电解液中滴加 0. l mol/L的 LiOH和 0. l mol/L的 HAc 溶液调节电解液的 pH为 4。 室温下， 在电压范围 1 .5-2. 1 V以 0.5 C倍率对电 池进行充放电。 LiMn 2 0 4 was used as a positive electrode active material, and a positive electrode active material, super-p carbon black, and a binder CMC-SB were uniformly mixed in a weight ratio of 83:10:7, and NMP was used as a dispersing agent to prepare a positive electrode slurry. The coating was applied to a positive electrode current collector stainless steel foil having a thickness of 50 μm. The surface active density of the positive electrode active material was 700 g/m 2 and the coating thickness was 0.4 mm. The stainless steel was not passivated, and then dried and pressed to obtain a positive electrode. The negative electrode is a metal zinc foil having a thickness of 40 μm, and the metal zinc is both a negative electrode active material and also serves as a negative electrode current collector. The diaphragm is a glass felt cloth. The electrolyte is an aqueous solution containing 1 mol/L of lithium acetate and 1.5 mol/L of zinc acetate, and the electrolyte is adjusted by adding 0.1 mol/L of LiOH and 0.1 mol/L of HAc solution to the electrolyte. The pH is 4. The battery was charged and discharged at a rate of 0.5 C in a voltage range of 1.5 to 2.1 V at room temperature.
实施例 6 中电池实验结果显示， 电池循环 320次的放电容量保持率以及 库伦效率均接近 100% , 表明电池具有非常优异的循环性能以及寿命。  The battery experiment results in Example 6 showed that the discharge capacity retention rate and the coulombic efficiency of the battery cycle were close to 100%, indicating that the battery has excellent cycle performance and longevity.
实施例 7  Example 7
在实施例 7 中， 将电池置于 55 °C下进行充放电， 以研究电池在高温下的 充放电性能， 电池其他组成以及测试方法同实施例 6。 图 8为实施例 7提供的电池的放电容量与循环次数的关系曲线， 从图中 可以看出， 电池在 55°C高温下， 依然具有良好的放电容量保持率， 电池循环 160次几乎没有明显的容量衰减。 In Example 7, the battery was charged and discharged at 55 ° C to investigate the charge and discharge performance of the battery at a high temperature. The other compositions and test methods of the battery were the same as those in Example 6. 8 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 7. As can be seen from the figure, the battery still has a good discharge capacity retention rate at a high temperature of 55 ° C, and the battery cycle is almost no significant 160 times. The capacity is attenuated.
实施例 8  Example 8
以 LiMn204 为正极活性物质， 将正极活性物质、 super-p 碳黑、 粘接剂 PVDF按照重量比例 83:10:7混合均匀，以 NMP作为分散剂，制得正极浆料， 均匀涂覆在厚度 30μηι 的正极集流体不锈钢网上， 正极活性物质的面密度为 300g/m2, 涂层的厚度为 0.2mm, 不锈钢不经过钝化， 随后干燥、 压制得到正 极。 负极为厚度 ΙΟμηι 的金属锌箔， 金属锌既是负极活性物质， 同时还兼做 负极集流体。 隔膜为玻璃毡布。 电解液为含有 lmol/L 醋酸锂和 1.5mol/L 醋 酸锌的水溶液， 通过向电解液中滴加 0. lmol/L 的 LiOH 和 0. lmol/L 的 HAc 溶液调节电解液的 pH为 4。 室温下， 在电压范围 1.5-2.1 V以 0.5C倍率对电 池进行充放电。 LiMn 2 0 4 was used as the positive electrode active material, and the positive electrode active material, super-p carbon black, and the binder PVDF were uniformly mixed at a weight ratio of 83:10:7, and NMP was used as a dispersing agent to prepare a positive electrode slurry, which was uniformly coated. The positive electrode active material has a surface density of 300 g/m 2 and a thickness of 0.2 mm. The stainless steel is not passivated, and then dried and pressed to obtain a positive electrode. The negative electrode is a metal zinc foil having a thickness of ΙΟμηι, which is both a negative electrode active material and also serves as a negative electrode current collector. The diaphragm is a glass felt cloth. The electrolyte was an aqueous solution containing 1 mol/L of lithium acetate and 1.5 mol/L of zinc acetate, and the pH of the electrolyte was adjusted to 4 by dropwise addition of 0.1 mol/L of LiOH and 0.1 mol/L of HAc solution to the electrolyte. The battery was charged and discharged at a rate of 0.5 C at a voltage range of 1.5-2.1 V at room temperature.
图 9为实施例 8提供的电池的放电容量与循环次数的关系曲线图， 从图中 可以看出， 电池循环 30次放电容量几乎没有衰减， 表明本发明提供的电池充 放电稳定性能良好。  Fig. 9 is a graph showing the relationship between the discharge capacity and the number of cycles of the battery provided in Example 8. As can be seen from the figure, the battery discharge cycle has almost no attenuation at 30 discharge capacities, indicating that the battery provided by the present invention has good charge and discharge stability.
实施例 9  Example 9
以 LiMn204为正极活性物质， 将正极活性物质、 super-p碳黑、 粘接剂 CMC-SBR按照重量比例90.5:1:2.5:6混合均匀， 以 NMP作为分散剂， 制得正极 浆料， 通过拉浆法使正极浆料均匀涂覆在厚度 0.1mm的正极集流体不锈钢网 上， 正极活性物质的面密度为 1500g/m2, 随后干燥、 压制得到正极， 涂层厚 度为 0.74mm。 LiMn 2 0 4 was used as the positive electrode active material, and the positive electrode active material, super-p carbon black, and binder CMC-SBR were uniformly mixed in a weight ratio of 90.5:1:2.5:6, and NMP was used as a dispersing agent to prepare a positive electrode slurry. The positive electrode slurry was uniformly coated on a positive electrode current collector stainless steel mesh having a thickness of 0.1 mm by a slurry drawing method, and the surface density of the positive electrode active material was 1500 g/m 2 , followed by drying and pressing to obtain a positive electrode having a coating thickness of 0.74 mm.
负极为厚度 50μηι的金属锌箔。 隔膜为玻璃纤维（AGM)。 电解液为含有 2mol/L硫酸锌和 0.5 mol/L硫酸锂的水溶液， 电解液 pH约为 3.5。  The negative electrode was a metal zinc foil having a thickness of 50 μm. The diaphragm is glass fiber (AGM). The electrolytic solution was an aqueous solution containing 2 mol/L of zinc sulfate and 0.5 mol/L of lithium sulfate, and the pH of the electrolyte was about 3.5.
室温下， 对电池进行充放电， 电压范围为 1.4-2. IV, 充电倍率均为 0.2C, 研究了在不同放电倍率下的电池性能。  The battery was charged and discharged at room temperature with a voltage range of 1.4-2. IV, and the charging rate was 0.2C. The battery performance at different discharge rates was investigated.
实施例 9中提供的电池分别以 0.25C、 1C、 2C和 4C进行放电， 电池以 0.25C 放电首次放电容量为 115mAh/g, 随着放电倍率增加， 电池首次放电容量略有 下降。  The batteries provided in Example 9 were discharged at 0.25 C, 1 C, 2 C and 4 C, respectively, and the battery was discharged at 0.25 C for the first discharge capacity of 115 mAh/g. As the discharge rate increased, the first discharge capacity of the battery slightly decreased.
尽管发明人已经对本发明的技术方案做了较详细的阐述和列举， 应当理 解， 对于本领域技术人员来说， 对上述实施例作出修改和 /或变通或者采用等 同的替代方案是显然的， 都不能脱离本发明精神的实质， 本发明中出现的术 语用于对本发明技术方案的阐述和理解， 并不能构成对本发明的限制。 Although the inventors have made a detailed description and enumeration of the technical solutions of the present invention, it should be understood that those skilled in the art may make modifications and/or modifications or adopts to the above embodiments. The same alternatives are obvious, and the spirit of the invention is not to be construed as a limitation of the invention.

Claims

权 利 要 求 书 Claim
1 . 一种电池， 包括正极、 负极和电解液，  A battery comprising a positive electrode, a negative electrode and an electrolyte,
所述正极包括正极集流体和形成于所述正极集流体上的涂层，所述涂层至 少包括参与正极反应的正极活性物质， 所述正极活性物质能够可逆脱出 - 嵌入离子；  The positive electrode includes a positive electrode current collector and a coating layer formed on the positive electrode current collector, the coating layer including at least a positive electrode active material participating in a positive electrode reaction, and the positive electrode active material capable of reversibly extracting-embeding ions;
所述负极至少包括负极集流体；  The anode includes at least a cathode current collector;
所述电解液包括溶剂和电解质， 所述溶剂选自水或醇， 所述电解质至少能 够电离出在充放电过程中在所述负极发生还原 -沉积和氧化-溶解的活性 离子；  The electrolyte includes a solvent and an electrolyte, and the solvent is selected from water or an alcohol, and the electrolyte is at least capable of ionizing an active ion that undergoes reduction-deposition and oxidation-dissolution at the anode during charge and discharge;
其特征在于： 所述涂层中正极活性物质的面密度范围为 100-3000g/m2。It is characterized in that the surface density of the positive electrode active material in the coating layer ranges from 100 to 3000 g/m 2 .
2.根据权利要求 1 中所述的电池， 其特征在于： 所述涂层中正极活性物质 的面密度为 300- 1500g/m2。 The battery according to claim 1, wherein the surface active density of the positive electrode active material in the coating layer is from 300 to 1,500 g/m 2 .
3.根据权利要求 1 中所述的电池， 其特征在于： 所述涂层的厚度范围为 40- 1 000μηι。  The battery according to claim 1, wherein the coating has a thickness ranging from 40 to 1 000 μm.
4. 一种电池， 包括正极、 负极和电解液，  4. A battery comprising a positive electrode, a negative electrode and an electrolyte,
所述正极包括正极集流体和形成于所述正极集流体上的涂层，所述涂层至 少包括参与正极反应的正极活性物质， 所述正极活性物质能够可逆脱出 - 嵌入离子；  The positive electrode includes a positive electrode current collector and a coating layer formed on the positive electrode current collector, the coating layer including at least a positive electrode active material participating in a positive electrode reaction, and the positive electrode active material capable of reversibly extracting-embeding ions;
所述负极至少包括负极集流体；  The anode includes at least a cathode current collector;
所述电解液包括溶剂和电解质， 所述溶剂选自水或醇， 所述电解质至少能 够电离出在充放电过程中在所述负极发生还原 -沉积和氧化-溶解的活性 离子；  The electrolyte includes a solvent and an electrolyte, and the solvent is selected from water or an alcohol, and the electrolyte is at least capable of ionizing an active ion that undergoes reduction-deposition and oxidation-dissolution at the anode during charge and discharge;
其特征在于： 所述涂层的厚度范围为 40- 1 000μηι。  It is characterized in that the thickness of the coating ranges from 40 to 1 000 μm.
5.根据权利要求 1 -4 中任一所述的电池， 其特征在于： 所述正极活性物质占 所述涂层的比重范围为 60-99%。  The battery according to any one of claims 1 to 4, wherein the positive electrode active material accounts for 60 to 99% of the specific gravity of the coating layer.
6.根据权利要求 1 -4 中任一所述的电池， 其特征在于： 所述涂层还包括导电 剂， 所述导电剂占所述涂层的比重范围为 0.5 -30%。  The battery according to any one of claims 1 to 4, wherein the coating further comprises a conductive agent, and the conductive agent accounts for 0.5 to 30% of the specific gravity of the coating.
7.根据权利要求 1 -4 中任一所述的电池， 其特征在于： 所述涂层还包括粘结 剂， 所述粘结剂占所述涂层的比重范围为 0.5 - 10%。  The battery according to any one of claims 1 to 4, wherein the coating further comprises an adhesive, the binder having a specific gravity ranging from 0.5 to 10%.
8.根据权利要求 1 -4 中任一所述的电池， 其特征在于： 所述正极集流体的厚 度范围为 5 - 100μηι。 根据权利要求 1 -4 中任一所述的电池， 其特征在于： 所述正极集流体的材 料选自碳基材料、金属或合金中的一种，其中，所述碳基材料选自玻璃碳、 石墨箔、 泡沫碳、 碳毡、 碳纤维中的一种； 其中， 所述金属选自 Al、 Fe、 Cu、 Pb、 Ti、 Cr、 Mo、 Co、 Ag或经过钝化处理的上述金属中的一种； 其 中， 所述合金选自不锈钢、 A1合金、 Ni合金、 Ti合金、 Cu合金、 Co合 金、 Ti-Pt合金、 Pt-Rh合金或经过钝化处理的上述合金中的一种。The battery according to any one of claims 1 to 4, wherein the positive electrode current collector has a thickness ranging from 5 to 100 μm. The battery according to any one of claims 1 to 4, wherein: the material of the cathode current collector is selected from one of a carbon-based material, a metal or an alloy, wherein the carbon-based material is selected from the group consisting of glassy carbon. One of graphite foil, foamed carbon, carbon felt, carbon fiber; wherein the metal is selected from the group consisting of Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or passivated metal One of the alloys selected from the group consisting of stainless steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or passivated alloy.
.根据权利要求 9所述的电池， 其特征在于： 所述不锈钢为不锈钢网， 所 述不锈钢网的规格选自 100 目 、 1 10 目 、 120 目 、 150 目 、 160 目 、 1 80 目 、 200 目 、 250 目 、 270 目或 300 目 。 The battery according to claim 9, wherein: the stainless steel is a stainless steel mesh, and the stainless steel mesh has a specification selected from the group consisting of 100 mesh, 10 mesh, 120 mesh, 150 mesh, 160 mesh, 180 mesh, 200. Head, 250 mesh, 270 mesh or 300 mesh.
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