CN104795561A - Layered O3-phase nickel oxide-contained positive electrode material and preparation method and application thereof - Google Patents

Layered O3-phase nickel oxide-contained positive electrode material and preparation method and application thereof Download PDF

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CN104795561A
CN104795561A CN201410361096.4A CN201410361096A CN104795561A CN 104795561 A CN104795561 A CN 104795561A CN 201410361096 A CN201410361096 A CN 201410361096A CN 104795561 A CN104795561 A CN 104795561A
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sodium
present
transition metal
active material
oxide
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CN104795561B (en
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胡勇胜
王跃生
徐淑银
陈立泉
黄学杰
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Institute of Physics of CAS
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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

Abstract

The invention discloses a layered O3-phase nickel oxide-contained positive electrode material, and a preparation method and an application of the material. The material is represented as a chemical general formula of Na<x>A<a>Ni<b>Ti<c>O<2-delta>. Ni, Mn and A together with six nearest oxygen atoms form an octahedral structure and a transition metal layer through edge-shared arrangement; six oxygen atoms in two transition metal layers form an octahedral structure; an alkali metal ion of Na+ is located between every two transition metal layers and occupies a position of the octahedral structure; A is one or more ions selected from Li+, Mg2+, B3+, Cu2+, Zn2+, Co3+, Al3+, V3+, Fe3+, Mn3+, and Mn4+; and the relationship among x, a, b, c, and delta satisfies x+ma+2b+4c=2(2-delta), and a+b+c=1, wherein x is more than 0.75 and less than 1; a is more than 0 and less than 0.6; b is more than 0 and less than 0.5; c is more than 0 and less than 0.6; and delta is more than -0.05 and less than 0.05.

Description

Nickeliferous oxide anode material of a kind of stratiform O3 phase and its production and use
Technical field
The present invention relates to field of material technology, particularly relate to nickeliferous oxide anode material of a kind of stratiform O3 phase and its production and use.
Background technology
To use in a large number as the reproducible clean energy resource such as solar energy, wind energy at present, but if this electric energy is directly inputted electrical network, very large impact can be brought to electrical network.So power conversion and storage have become wherein key issue.Thing followed problem how to modulate to store this time dependent electric energy.Electric energy conversion can become chemical energy to store by electrochemical energy storage efficiently, and changes into stable electric power output again.Therefore develop cheapness, extensive research that safety, high power capacity, good rate capability, secondary cell that voltage range is suitable cause people.Lithium ion battery has high energy density, high operating voltage, stable circulation, and is widely used, little household electrical appliance be applied to high energy density, powerful application apparatus, as electric automobile, national grid etc.But lithium resource is limited, cost intensive, makes battery cost raise.And compared with lithium, purify simple, with low cost, negative pole of the rich content of sodium in the earth's crust, exploitation can use more cheap aluminium foil as collector, chemical property shows a lot of performances similar to lithium, and also its memory mechanism is similar to lithium.Therefore, sodium ion secondary causes people again research interest as effective memory device is developed.
At present, sodium ion battery electrode material receives to be studied widely, and reports a large amount of sodium-ion battery positive material.Mainly concentrate on oxide and phosphate two parts of transition metal.Transition metal mainly comprises: cobalt, nickel, manganese, chromium, vanadium, iron.Vanadium and chromium are all toxic element, to human body and environmental hazard large.Na in the oxide xcoO 2be the positive electrode be used in the earliest in sodium ion secondary battery, but cobalt is expensive, thus causes battery cost to increase, and current potential is between 2.2-3.8V, average potential is lower.Although the low price of manganese, occurring in nature rich content, in the oxide containing pure manganese, general manganic Jahn-Teller effect is obvious.Na 0.44mnO 2first all charging capacitys are lower, only have 45mAh/g.And the oxide NaMnO of another kind of manganese 2although Capacity Ratio is higher, it is extremely unstable in atmosphere.Therefore will realize the practical of sodium ion secondary battery, positive electrode also needs new research and probe, and find specific capacity high, coulombic efficiency is high, low-cost electrode material.
Summary of the invention
The invention provides nickeliferous oxide anode material of a kind of stratiform O3 phase and its production and use, this material has stratiform O3 phase structure, capacity is higher, voltage range is suitable, relative inexpensiveness, first all coulombic efficiencies are high, and this positive electrode in atmosphere can stable existence, may be used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
First aspect, embodiments provide the nickeliferous oxide anode material of a kind of stratiform O3 phase, the chemical general formula of layered oxide material is: Na xa ani bti co 2-δ;
Wherein, Ni, Ti are transition metal, and A is element transition metal position being carried out to doped and substituted; Ni, Mn and A form octahedral structure with six oxygen atoms of arest neighbors respectively, and multiple described octahedral structure altogether limit arrangement forms transition metal layer; Six oxygen atoms in two-layer transition metal layer form octahedral structure, alkali metal ion Na +between every two-layer described transition metal layer, occupy octahedral site; Described A is Li +, Mg 2+, B 3+, Cu 2+, Zn 2+, Co 3+, Al 3+, V 3+, Fe 3+, Mn 3+, Mn 4+in one or more; The valent state of described A is m, and described relation between x, a, b, c, δ and m meets x+ma+2b+4c=2 (2-δ), and meets a+b+c=1; Wherein, 0.75<x<1,0<a<0.6,0<b<0.5,0<c<0.6 ,-0.05< δ <0.05.
Optionally, at described chemical general formula Na xa ani bti co 2-δin, preferably 0.8≤x<1,0.01≤a<0.5,0.2≤b<0.5,0<c<0.5 ,-0.02< δ <0.02.Second aspect, embodiments provide a kind of preparation method of nickeliferous oxide anode material, described method is solid phase method, comprising:
Contain the sodium carbonate and the required oxide of stoichiometric doping metals and the oxide of A of the stoichiometry 102wt% of required sodium ~ 105wt% are mixed according to the stoichiometric proportion of positive active material, after grinding evenly, obtains precursor powder; Described A is Li +, Mg 2+, B 3+, Cu 2+, Zn 2+, Co 3+, Al 3+, V 3+, Fe 3+, Mn 3+, Mn 4+in one or more;
Gained precursor powder is placed in crucible, heat treatment 5 ~ 24 hours in the air atmosphere of 900 DEG C ~ 1000 DEG C, grinding, obtains layered oxide material.
Second aspect, embodiments provide a kind of preparation method of nickeliferous oxide anode material, described method is sol-gel process, comprising:
The nitrate of the nitrate of the acetate of the sodium ion of the stoichiometry 102wt% of required sodium ~ 105wt% and required stoichiometric nickel, butyl titanate and A is dissolved in absolute ethyl alcohol or deionized water respectively, and adds citric acid and form aqueous precursor gel; Described A is Li +, Mg 2+, B 3+, Cu 2+, Zn 2+, Co 3+, Al 3+, V 3+, Fe 3+, Mn 3+, Mn 4+in one or more;
Described aqueous precursor gel is placed in crucible, and under the air atmosphere of 250 DEG C ~ 500 DEG C, preliminary treatment 2 ~ 6 hours, obtains preliminary treatment powder;
By the heat treatment 5 ~ 20 hours at 800 DEG C ~ 1000 DEG C of described preliminary treatment powder, grinding, obtains layered oxide material.
Fourth aspect, embodiments provides a kind of anode pole piece of sodium ion secondary battery, and described anode pole piece comprises:
Collector, be coated on conductive additive, binding agent and the nickeliferous oxide anode material as described in above-mentioned first aspect on described collector.
Optionally, described conductive additive comprises: one or more during carbon black, acetylene black, graphite powder, carbon nano-tube, graphite are rare.
Optionally, described binding agent comprises:
Kynoar PVDF, one or more solution in polytetrafluoroethylene PTFE, sodium alginate, sodium carboxymethylcellulose CMC, styrene butadiene rubber sbr or 1-METHYLPYRROLIDONE NMP.
Optionally, described collector comprises: any one in aluminium foil, nickel screen, titanium net, stainless (steel) wire, nickel foam.
5th aspect, embodiments provides a kind of sodium ion secondary battery comprising anode pole piece described in above-mentioned fourth aspect.
6th aspect, the bright embodiment of this law provides the purposes of the sodium ion secondary battery described in a kind of above-mentioned 5th aspect, and described sodium ion secondary battery is used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
The nickeliferous oxide anode material of stratiform O3 phase that the embodiment of the present invention provides, there is stratiform O3 phase structure, in atmosphere can stable existence, can be applied in sodium ion secondary battery, apply the sodium ion secondary battery of the nickeliferous oxide anode material of stratiform O3 phase of the present invention, capacity is higher, voltage range is suitable, relative inexpensiveness, first all coulombic efficiencies are high, may be used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
Accompanying drawing explanation
Below by drawings and Examples, the technical scheme of the embodiment of the present invention is described in further detail.
X-ray diffraction (XRD) collection of illustrative plates of the nickeliferous oxide anode material of a kind of stratiform O3 phase that Fig. 1 provides for the embodiment of the present invention 1;
The SEM figure of the nickeliferous oxide anode material of a kind of stratiform O3 phase that Fig. 2 provides for the embodiment of the present invention 1;
The crystal structure figure of the nickeliferous oxide anode material of a kind of stratiform O3 phase that Fig. 3 provides for the embodiment of the present invention 1;
Preparation method's flow chart of the nickeliferous oxide anode material of a kind of stratiform O3 phase that Fig. 4 provides for the embodiment of the present invention 2;
Preparation method's flow chart of the nickeliferous oxide anode material of a kind of stratiform O3 phase that Fig. 5 provides for the embodiment of the present invention 3;
The charging and discharging curve figure of a kind of sodium-ion battery that Fig. 6 provides for the embodiment of the present invention 4;
The charging and discharging curve figure of a kind of sodium-ion battery that Fig. 7 provides for the embodiment of the present invention 5;
The charging and discharging curve figure of a kind of sodium-ion battery that Fig. 8 provides for the embodiment of the present invention 6;
The charging and discharging curve figure of a kind of sodium-ion battery that Fig. 9 provides for the embodiment of the present invention 7;
The charging and discharging curve figure of a kind of sodium-ion battery that Figure 10 provides for the embodiment of the present invention 8;
The charging and discharging curve figure of a kind of sodium-ion battery that Figure 11 provides for the embodiment of the present invention 9;
The charging and discharging curve figure of a kind of sodium-ion battery that Figure 12 provides for the embodiment of the present invention 10.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not intended to limit the scope of the invention.
Embodiment 1
The embodiment of the present invention 1 provides the nickeliferous oxide anode material of a kind of stratiform O3 phase, and its chemical general formula is: Na xa ani bti co 2-δ;
Wherein, Ni, Ti are transition metal, and A is element transition metal position being carried out to doped and substituted; Described A is Li +, Mg 2+, B 3+, Cu 2+, Zn 2+, Co 3+, Al 3+, V 3+, Fe 3+, Mn 3+, Mn 4+in one or more; The valent state of described A is m, and described relation between x, a, b, c, δ and m meets x+ma+2b+4c=2 (2-δ), and meets a+b+c=1; Wherein, 0.75<x<1,0<a<0.6,0<b<0.5,0<c<0.6 ,-0.05< δ <0.05.
At Na xa ani bti co 2-δstructure in, Ni, Mn and A form octahedral structure with six oxygen atoms of arest neighbors respectively, and multiple described octahedral structure altogether limit arrangement forms transition metal layer; Six oxygen atoms in two-layer transition metal layer form octahedral structure, alkali metal ion Na +between every two-layer described transition metal layer, occupy octahedral site, thus form stratiform O3 phase structure.
Below, with Na 0.90mn 0.01ni 0.45ti 0.54o 2for the structure of example to the nickeliferous oxide anode material of layered O3 phase is described in detail.
Figure 1 shows that Na 0.90mn 0.01ni 0.45ti 0.54o 2x-ray diffraction (X-ray diffraction, XRD) collection of illustrative plates, as can be seen from XRD collection of illustrative plates, the Na that the present embodiment provides 0.90mn 0.01ni 0.45ti 0.54o 2for stratiform O3 phase structure.
Figure 2 shows that Na 0.90mn 0.01ni 0.45ti 0.54o 2eSEM (SEM) figure; Figure 3 shows that Na 0.90mn 0.01ni 0.45ti 0.54o 2space structure schematic diagram.
The nickeliferous oxide anode material of stratiform O3 phase that the embodiment of the present invention provides, has stratiform O3 phase structure, in atmosphere can stable existence, can be applied in sodium ion secondary battery as positive electrode active materials.
Embodiment 2
Present embodiments provide the preparation method of the nickeliferous oxide anode material of a kind of stratiform O3 phase, be specially solid phase method, as shown in Figure 4, comprising:
Step 401, mixes contain the sodium carbonate and the required oxide of stoichiometric doping metals and the oxide of A of the stoichiometry 102wt% of required sodium ~ 105wt% according to the stoichiometric proportion of positive active material, obtains precursor powder after grinding evenly;
Concrete, described A is Li +, Mg 2+, B 3+, Cu 2+, Zn 2+, Co 3+, Al 3+, V 3+, Fe 3+, Mn 3+, Mn 4+in one or more.
Step 402, is placed in crucible by gained precursor powder, heat treatment 5 ~ 24 hours in the air atmosphere of 900 DEG C ~ 1000 DEG C, and grinding, obtains layered oxide material.
The preparation method that the present embodiment provides, can be used in the nickeliferous oxide anode material of stratiform O3 phase prepared described in above-described embodiment 1.The method that the present embodiment provides is simple, with low cost, can be suitable for large-scale application.
Embodiment 3
Present embodiments provide the preparation method of the nickeliferous oxide anode material of a kind of stratiform O3 phase, be specially sol-gel process, as shown in Figure 5, comprising:
Step 501, the nitrate of the nitrate (as nickel nitrate) of the acetate of the sodium ion of the stoichiometry 102wt% of required sodium ~ 105wt% and required stoichiometric nickel, butyl titanate and A is dissolved in absolute ethyl alcohol or deionized water respectively, and adds citric acid and form aqueous precursor gel;
Concrete, described A is Li +, Mg 2+, B 3+, Cu 2+, Zn 2+, Co 3+, Al 3+, V 3+, Fe 3+, Mn 3+, Mn 4+in one or more.
Step 502, is placed in crucible by described aqueous precursor gel, and under the air atmosphere of 250 DEG C ~ 500 DEG C, preliminary treatment 2 ~ 6 hours, obtains preliminary treatment powder;
Step 503, by the heat treatment 5 ~ 20 hours at 800 DEG C ~ 1000 DEG C of described preliminary treatment powder, grinding, obtains layered oxide material.
The preparation method that the present embodiment provides, can be used in the nickeliferous oxide anode material of stratiform O3 phase prepared described in above-described embodiment 1.The method that the present embodiment provides is simple, with low cost, can be suitable for large-scale application.
The method provided with multiple instantiation application the above embodiment of the present invention below prepares the detailed process of the nickeliferous oxide anode material of embodiment 1 laminate O3 phase, and is applied to method and the battery behavior of secondary cell.
Embodiment 4
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), NiO, MnO 2and TiO 2stoichiometrically mix, wherein Na excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma; Precursor species compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained green ceramic sheet is for subsequent use after grinding, is active material Na of the present invention 0.90mn 0.01ni 0.45ti 0.54o 2.
Above-mentioned active material is prepared into sodium-ion battery as positive electrode.Concrete steps are: by the active material Na prepared 0.90mn 0.01ni 0.45ti 0.54o 2powder mixes according to the mass ratio of 70:20:10 with acetylene black, binding agent Kynoar (PVDF), add appropriate 1-METHYLPYRROLIDONE (NMP) Solutions Solution, in the environment of air drying, grinding forms slurry, then slurry is evenly coated in current collector aluminum foil, and dry under infrared lamp, be cut into the pole piece of 8 × 8mm.Under vacuum in 100 DEG C of dryings 10 hours, be transferred to glove box immediately for subsequent use.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal sheet as to electrode, the NaClO of 1M 4/ ethylene carbonate (EC): diethyl carbonate (DEC) solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to test, discharging by voltage is 2.5V, and charging by voltage is 4.2V, and all tests are all carried out under C/10 current density.Test result is shown in Fig. 6.First week respectively, the charge and discharge cycles curve of second week, 4th week and the tenth week.Found out by Fig. 6, the voltage range of main capacity is at 2.8-4.2V, and its first all charging capacity can reach 118mAh/g, specific discharge capacity 103.5mAh/g, and first all coulombic efficiencies are about 87.7%, the tenth week charge specific capacity 107mAh/g, specific discharge capacity 102 mAh/g.
Embodiment 5
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), NiO, Mn 2o 3and TiO 2stoichiometrically mix, wherein Na content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained chocolate brown powder is for subsequent use after grinding, is active material Na of the present invention 0.85mn 0.05ni 0.42ti 0.555o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.1V, and test result is shown in Fig. 7.Be respectively first week charging curve and first week discharge curve.Found out by Fig. 7, its first all charging capacity is 98mAh/g, and first all discharge capacities can reach 90mAh/g, and first all coulombic efficiencies are about 91.8%.
Embodiment 6
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), NiO, Co 2o 3and TiO 2stoichiometrically mix, wherein sodium content excessive 5%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained chocolate brown powder is for subsequent use after grinding, is active material Na of the present invention 0.80co 0.10ni 0.35ti 0.55o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4, and test voltage scope is 2.5V-4.1V, and test result is shown in Fig. 8.Be respectively first week charging curve and first week discharge curve.Found out by Fig. 8, its first all charging capacity is 90mAh/g, and first all discharge capacities can reach 86mAh/g, and first all coulombic efficiencies are about 95%.
Embodiment 7
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), NiO, Fe 2o 3and TiO 2stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained chocolate brown powder is for subsequent use after grinding, is active material Na of the present invention 0.75fe 0.12ni 0.315ti 0.565o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.1V, and test result is shown in Fig. 9.Be respectively first week charging curve and first week discharge curve.Found out by Fig. 9, its first all charging capacity is 80mAh/g, and first all discharge capacities can reach 76mAh/g, and first all coulombic efficiencies are about 95%.
Embodiment 8
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), NiO, B 2o 3and TiO 2stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained chocolate brown powder is for subsequent use after grinding, is active material Na of the present invention 0.95b 0.05ni 0.40ti 0.595o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.2V, and test result is shown in Figure 10.Be respectively first week charging curve and first week discharge curve.Found out by Figure 10, its first all charging capacity is 110mAh/g, and first all discharge capacities can reach 102.5mAh/g, and first all coulombic efficiencies are about 93.1%.
Embodiment 9
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), NiO, Al 2o 3and TiO 2stoichiometrically mix, wherein sodium content excessive 4%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained chocolate brown powder is for subsequent use after grinding, is active material Na of the present invention 0.82al 0.08ni 0.42ti 0.50o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.2V, and test result is shown in Figure 11.Be respectively first week charging curve and first week discharge curve.Found out by Figure 11, its first all charging capacity is 90mAh/g, and first all discharge capacities can reach 81mAh/g, and first all coulombic efficiencies are about 90%.
Embodiment 10
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), NiO, Mn 2o 3, Al 2o 3and TiO 2stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained chocolate brown powder is for subsequent use after grinding, is active material Na of the present invention 0.86al 0.02mn 0.03ni 0.38ti 0.57o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.1V, and test result is shown in Figure 12.Be respectively first week charging curve and first week discharge curve.Found out by Figure 12, its first all charging capacity is 98mAh/g, and first all discharge capacities can reach 92mAh/g, and first all coulombic efficiencies are about 93.8%.
Embodiment 11
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), Al 2o 3, NiO, Mn 2o 3and TiO 2stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained green flour tailpiece is for subsequent use after grinding, is active material Na of the present invention 0.85al 0.05mn 0.30ni 0.425ti 0.225o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out charge-discharge test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.2V, and test result sees the following form 1.
Embodiment 12
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), ZnO, NiO and TiO 2stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained green flour tailpiece is for subsequent use after grinding, is active material Na of the present invention 0.90zn 0.01co 0.04ni 0.40ti 0.55o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.1V, the results are shown in following table 1.
Embodiment 13
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), (MgCO 3) 4mg (OH) 25H 2o (analyzing pure), NiO and TiO 2stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained green flour tailpiece is for subsequent use after grinding, is active material Na of the present invention 0.90mg 0.05ni 0.40ti 0.55o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.1V, the results are shown in following table 1.
Embodiment 14
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), Li 2cO 3(analyzing pure), NiO and TiO 2stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained green flour tailpiece is for subsequent use after grinding, is active material Na of the present invention 0.80li 0.10ni 0.40ti 0.50o 1.98.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.2V, the results are shown in following table 1.
Embodiment 15
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), Al 2o 3, NiO and TiO 2stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained green flour tailpiece is for subsequent use after grinding, is active material Na of the present invention 0.95al 0.05co 0.05ni 0.40ti 0.50o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.2V, the results are shown in following table 1.
Embodiment 16
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), NiO, MnO 2and TiO 2stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 24 hours under 1000 degrees Celsius, gained pale green powder sheet is for subsequent use after grinding, is active material Na of the present invention 0.92mn 0.04ni 0.46ti 0.50o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.2V, the results are shown in following table 1.
Embodiment 17
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), ZnO, NiO, TiO 2and Mn 2o 3stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 18 hours under 980 degrees Celsius, gained green flour tailpiece is for subsequent use after grinding, is active material Na of the present invention 0.90zn 0.05mn 0.20ni 0.40ti 0.35o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.2V, the results are shown in following table 1.
Embodiment 18
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), MgO, NiO, TiO 2and Mn 2o 3stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained green flour tailpiece is for subsequent use after grinding, is active material Na of the present invention 0.80zn 0.02mn 0.03ni 0.35ti 0.60o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.2V, the results are shown in following table 1.
Embodiment 19
The present embodiment adopts solid phase method to prepare active material, and concrete steps are: by Na 2cO 3(analyzing pure), B 2o 3, NiO, MnO 2and TiO 2stoichiometrically mix, wherein sodium content excessive 2%, mixed grinding half an hour in agate mortar, obtain presoma, presoma compressing tablet is transferred to Al 2o 3in crucible, in Muffle furnace, process 20 hours under 1000 degrees Celsius, gained green flour tailpiece is for subsequent use after grinding, is active material Na of the present invention 0.80b 0.04mn 0.08ni 0.38ti 0.50o 2.
Above-mentioned positive active material is prepared into sodium-ion battery, and carries out electro-chemical test.Its method of testing is substantially the same manner as Example 4.Test voltage scope is 2.5V-4.2V, the results are shown in following table 1.
Table 1
Although above-described embodiment 5-19 illustrates the detailed process of the nickeliferous oxide anode material of preparation stratiform O3 phase with the solid phase method applied the embodiment of the present invention 2 and provide, and be applied to method and the battery behavior of secondary cell, but do not limit above-described embodiment 5-19 and can only apply solid phase method that the embodiment of the present invention 2 provides to carry out material preparation, those skilled in the art easily expect, the sol-gel process that the embodiment of the present invention 3 also can be adopted to provide is to prepare the nickeliferous oxide anode material of stratiform O3 phase of above-described embodiment 5-19.
The nickeliferous oxide anode material of one provided by the invention, has O3 layer structure, capacity is higher, voltage range is suitable, relative inexpensiveness, first all coulombic efficiencies be high, and this positive electrode in atmosphere can stable existence.In addition, for existing O3 phase material, such as Na content is 1, and general formula is NaMO 2the material of (wherein M is transition metal) is the chemicals of 1 for Na, often unstable in atmosphere.But the Na that Na content provided by the invention is less than 1 xa ani bti co 2-δ(0.75<x<1), but can with O3 phase structure stable existence, and also more stable in atmosphere.
The nickeliferous oxide anode material of stratiform O3 phase that the embodiment of the present invention provides, has stratiform O3 phase structure, in atmosphere can stable existence, and can be applied in sodium ion secondary battery, its operating voltage range is between 3.0 ~ 4.2V, and average voltage is about 3.4V.Apply the sodium ion secondary battery of the nickeliferous oxide anode material of stratiform O3 phase of the present invention, capacity is higher, voltage range is suitable, relative inexpensiveness, first all coulombic efficiencies are high, may be used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
Above-described embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only the specific embodiment of the present invention; the protection range be not intended to limit the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. the nickeliferous oxide anode material of stratiform O3 phase, is characterized in that, the chemical general formula of described material is: Na xa ani bti co 2-δ;
Wherein, Ni, Ti are transition metal, and A is element transition metal position being carried out to doped and substituted; Ni, Mn and A form octahedral structure with six oxygen atoms of arest neighbors respectively, and multiple described octahedral structure altogether limit arrangement forms transition metal layer; Six oxygen atoms in two-layer transition metal layer form octahedral structure, alkali metal ion Na +between every two-layer described transition metal layer, occupy octahedral site; Described A is Li +, Mg 2+, B 3+, Cu 2+, Zn 2+, Co 3+, Al 3+, V 3+, Fe 3+, Mn 3+, Mn 4+in one or more; The valent state of described A is m, and described relation between x, a, b, c, δ and m meets x+ma+2b+4c=2 (2-δ), and meets a+b+c=1; Wherein, 0.75<x<1,0<a<0.6,0<b<0.5,0<c<0.6 ,-0.05< δ <0.05.
2. nickeliferous oxide anode material according to claim 1, is characterized in that, at described chemical general formula Na xa ani bti co 2-δin, preferably 0.8≤x<1,0.01≤a<0.5,0.2≤b<0.5,0<c<0.5 ,-0.02< δ <0.02.
3., as a preparation method for above-mentioned nickeliferous oxide anode material according to claim 1, it is characterized in that, described method is solid phase method, comprising:
Contain the sodium carbonate and the required oxide of stoichiometric doping metals and the oxide of A of the stoichiometry 102wt% of required sodium ~ 105wt% are mixed according to the stoichiometric proportion of positive active material, after grinding evenly, obtains precursor powder; Described A is Li +, Mg 2+, B 3+, Cu 2+, Zn 2+, Co 3+, Al 3+, V 3+, Fe 3+, Mn 3+, Mn 4+in one or more;
Gained precursor powder is placed in crucible, heat treatment 5 ~ 24 hours in the air atmosphere of 900 DEG C ~ 1000 DEG C, grinding, obtains layered oxide material.
4., as a preparation method for above-mentioned nickeliferous oxide anode material according to claim 1, it is characterized in that, described method is sol-gel process, comprising:
The nitrate of the nitrate of the acetate of the sodium ion of the stoichiometry 102wt% of required sodium ~ 105wt% and required stoichiometric nickel, butyl titanate and A is dissolved in absolute ethyl alcohol or deionized water respectively, and adds citric acid and form aqueous precursor gel; Described A is Li +, Mg 2+, B 3+, Cu 2+, Zn 2+, Co 3+, Al 3+, V 3+, Fe 3+, Mn 3+, Mn 4+in one or more;
Described aqueous precursor gel is placed in crucible, and under the air atmosphere of 250 DEG C ~ 500 DEG C, preliminary treatment 2 ~ 6 hours, obtains preliminary treatment powder;
By the heat treatment 5 ~ 20 hours at 800 DEG C ~ 1000 DEG C of described preliminary treatment powder, grinding, obtains layered oxide material.
5. an anode pole piece for sodium ion secondary battery, is characterized in that, described anode pole piece comprises:
Collector, be coated on conductive additive on described collector, binding agent and as above-mentioned nickeliferous oxide anode material according to claim 1.
6. anode pole piece according to claim 5, is characterized in that, described conductive additive comprises: one or more during carbon black, acetylene black, graphite powder, carbon nano-tube, graphite are rare.
7. anode pole piece according to claim 5, is characterized in that, described binding agent comprises:
Kynoar PVDF, one or more solution in polytetrafluoroethylene PTFE, sodium alginate, sodium carboxymethylcellulose CMC, styrene butadiene rubber sbr or 1-METHYLPYRROLIDONE NMP.
8. anode pole piece according to claim 5, is characterized in that, described collector comprises: any one in aluminium foil, nickel screen, titanium net, stainless (steel) wire, nickel foam.
9. one kind comprises the sodium ion secondary battery of the anode pole piece described in the arbitrary claim of the claims 5-8.
10. the purposes as above-mentioned sodium ion secondary battery according to claim 9, it is characterized in that, described sodium ion secondary battery is used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
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CN105914354A (en) * 2016-05-09 2016-08-31 北京工业大学 Sodium-rich type titanium matrix layered solid solution electrode material for room-temperature sodium ion battery and preparation method
CN106025252A (en) * 2016-05-09 2016-10-12 北京工业大学 Sodium-lacking type Ti laminated solid solution electrode active material and preparation method
CN106025252B (en) * 2016-05-09 2019-04-12 北京工业大学 Owe sodium form Ti base shape solid solution electrode active material and preparation method
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CN112670497A (en) * 2019-09-27 2021-04-16 宁德时代新能源科技股份有限公司 Positive electrode active material for sodium ion battery, battery module, battery pack, and device each made of the active material
CN110783525A (en) * 2019-10-31 2020-02-11 溧阳中科海钠科技有限责任公司 Positive electrode additive for sodium ion battery, battery positive electrode, sodium ion battery and application
CN111762820A (en) * 2020-07-14 2020-10-13 宁夏大学 Layered manganese-based positive electrode material of sodium-ion battery and preparation method thereof
CN114790013A (en) * 2021-01-26 2022-07-26 中国科学院物理研究所 Sodium ion battery positive electrode active material capable of self-supplementing sodium, and preparation method and application thereof
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