CN107275620A - One kind is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material and preparation method thereof - Google Patents

One kind is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material and preparation method thereof Download PDF

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CN107275620A
CN107275620A CN201710544943.4A CN201710544943A CN107275620A CN 107275620 A CN107275620 A CN 107275620A CN 201710544943 A CN201710544943 A CN 201710544943A CN 107275620 A CN107275620 A CN 107275620A
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nickel
lithium
salt
positive pole
ion battery
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杨成浩
欧星
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Guangzhou Towards Lithium Amperex Technology Ltd
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Guangzhou Towards Lithium Amperex Technology Ltd
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

Modification lithium-ion battery stratiform nickel-rich positive pole material and preparation method thereof is mixed with the invention discloses one kind.The chemical formula of the lithium ion battery stratiform nickel-rich positive pole material is：MOx·LiNi1‑a‑b‑c‑dCoaMnbAlcMdO2, MOxFor surface modification layer material.The present invention prepares by the preparation of liquid phase presoma, high temperature solid-phase sintering and surface modification method and is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material.Doping vario-property has good lithium ion conductive, is conducive to the deintercalation of lithium ion, can greatly improve the high rate performance of stratiform nickel-rich positive pole material, and then improve the power density and energy density of anode material for lithium-ion batteries.Material surface alkali content can be reduced using surface coating decoration, the generation of side reaction is reduced, the cycle performance and security performance of stratiform nickel-rich positive pole material is improved, process is simple, easy control of structure, industrialization large-scale production can be realized.

Description

One kind is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material and its preparation Method
Technical field
The invention belongs to the preparing technical field of lithium ion battery electrode material, and in particular to one kind is mixed with modified lithium Ion battery stratiform nickel-rich positive pole material and preparation method thereof.
Background technology
In recent years, the demand for development brought with the technological innovation of electric automobile, to the lithium ion battery of electrokinetic cell Energy density proposes higher requirement.Stratiform nickel-rich positive pole material LiNixCoyMz(wherein, 0.5≤x≤1, M be Mn, Al, One or more in Zn, Mg, Ti, Zr and V), it is lithium ion power battery cathode material of greatest concern in recent years, possesses energy The features such as amount is high, cost is low, security is good, shows excellent chemical property, is expected to turn into the power that future market is dominated Cell positive material.
But, stratiform nickel-rich positive pole material is with the increase of nickel content, although specific capacity increase, its there is inherent shortcoming and Recurring structure changes, and has great difficulty in commercial application.Stratiform nickel-rich positive pole material is in cyclic process, particularly high pressure Under the specific conditions such as high temperature, the Ni after oxidation4+Can and electrolyte occur side reaction, cause structure collapses and irreversible, and material Expect direct impedance increase, bring serious safety issue, be the key for restricting its large-scale application.In addition, rich nickel positive pole material Lithium nickel mixing occurs during the course of the reaction for material, causes the abjection of active oxygen and generates a large amount of lithium residue Li in material surface2O or LiOH, and substantial amounts of H is absorbed during ingress of air2O/CO2, a large amount of lithium residues and moisture, extreme influence material are accumulated in material surface Processing characteristics, while producing the flatulence problem of material, cause cycle performance to decay, the overall chemical property of final material Deteriorate and fail.
Under normal circumstances, metal ion mixing is a kind of side for being effectively improved the rich nickel material long-term cycle stability of stratiform Method, but material and the direct contact of air or electrolyte, the generation of reduction material surface lithium residue can not be reduced.Although table Face residue can increase washing the step in preparation process, but rich nickel material is very sensitive to moisture, easily occur de- lithium Reaction and surface crystal structure is destroyed, so as to reduce the chemical property of material.Accordingly, it would be desirable to further use surface Cladding carrys out modified layered nickel-rich positive pole material to modify, and is conducive to the deintercalation of lithium ion, reduces the excessive lithium residue of material surface.
Therefore be mixed with modification lithium-ion battery stratiform nickel-rich positive pole material and preparation method thereof to lift material there is provided one kind The chemical property and process safety performance of material are very necessary.
The content of the invention
Modification lithium-ion battery stratiform nickel-rich positive pole material and its preparation are mixed with it is an object of the invention to provide one kind Method, the preparation technology to existing lithium ion battery nickel-rich positive pole material is improved, to improve the rich nickel of lithium ion battery just The cyclical stability and high rate performance of pole material, improve the electricity of material charge-discharge test under the harsh conditions such as high pressure or high temperature Chemical property, increases the energy density of material, it is adaptable to industrial applications.
The purpose of the present invention is realized by following technological means.
A kind of preparation method for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, including following step are provided Suddenly：
1) nickel salt, cobalt salt, manganese salt, aluminium salt and M metal salts are weighed to be dissolved separately in deionized water, concentration is configured to respectively It is 0.05-2mol/L salting liquid；The nickel salt, cobalt salt, manganese salt, aluminium salt and M metal salts are according to nickelic layered cathode material Material precursor chemical formula Ni1-a-b-c-dCoaMnbAlcMd(OH)2The mol ratio of middle Ni, Co, Mn, Al and M element is weighed, wherein a, b, C, d, x are molal quantity, 0<A≤0.3,0<B≤0.2,0<C≤0.05,0<D≤0.05 and 0<A+b+c+d≤0.5, M be metal from One or more in sub- Zn, Mg, Ti, Zr and V；
2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration For 0.2-2mol/L, the molar concentration of ammoniacal liquor is 0.1-1mol/L；
3) by step 2) gained mixed ammonium/alkali solutions be added in reactor, the volume of mixed ammonium/alkali solutions accounts for reactor volume %-80%, and control the pH value of liquid in reactor between 8-12, temperature is between 40-80 DEG C；
4) by step 1) nickel salt, cobalt salt, manganese salt, aluminium salt and the M metal salt solutions that prepare by peristaltic pump respectively at the uniform velocity Add in reactor, control the pH value of liquid in reactor between 8-12 in whole process, temperature is between 40-80 DEG C；
5) treat that nickel salt, cobalt salt, manganese salt, aluminium salt and M metal salts are added completely into, it is still aging 8-24 hours after, then will be heavy Form sediment and filter, wash, drying；
6) by step 5) obtain presoma Ni1-a-b-c-dCoaMnbAlcMd(OH)2It is well mixed with lithium source, lithium source, The mol ratio of presoma metal ion is Li：(Ni+Co+Mn+Al+M)=(1-1.1):1；Then material is put into tube furnace, Heat 3-10 hours in 300-600 DEG C under oxygen atmosphere, then sintered 10-25 hours at 700-1000 DEG C, it is naturally cold But to room temperature, the lithium ion battery stratiform nickel-rich positive pole material LiNi of M metal ion mixings is produced1-a-b-c-dCoaMnbAlcMdO2；
7) by the LiNi after doping1-a-b-c-dCoaMnbAlcMdO2Positive electrode is added in dispersant solution, ultrasonically treated 0.5-1 hours；
8) and then M metal salts are weighed add in deionized water and be made into M metal salt solutions, M metal salt solutions concentration is 0.1- 3mol/L；
The M metal salt solutions configured are added drop-wise to step 7) solution in, the solvent evaporated at 80-100 DEG C, in 100- Dry 8-20 hours, then crush at 120 DEG C, then sintered 1-8 hours under 300 DEG C -600 DEG C of air atmosphere, that is, mixed Miscellaneous coating modification lithium ion battery stratiform nickel-rich positive pole material MOx·LiNi1-a-b-c-dCoaMnbAlcMdO2。
It is preferred that, above-mentioned nickel salt is the one or more in nickel sulfate, nickel nitrate, nickel chloride, nickel oxalate and nickel acetate.
It is preferred that, above-mentioned cobalt salt is the one or more in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt oxalate and cobalt acetate.
It is preferred that, above-mentioned manganese salt is the one or more in manganese sulfate, manganese nitrate, manganese chloride and manganese acetate；Aluminium salt is sulphur One or more in sour aluminium, aluminum nitrate and aluminium chloride；M metal salts are one kind in zinc salt, magnesium salts, titanium salt, zirconates or vanadic salts Or it is a variety of.
It is preferred that, above-mentioned steps 2) described in alkaline solution be sodium hydroxide solution and potassium hydroxide solution in one kind or Two kinds；When alkaline solution is sodium hydroxide solution, the mol ratio of sodium hydroxide and ammoniacal liquor is 2：1.
It is preferred that, above-mentioned steps 6) lithium source be lithium hydroxide, lithium oxalate, lithium carbonate, lithium acetate and lithium nitrate in one Plant or a variety of.
It is preferred that, above-mentioned steps 7) dispersant be one kind in ethanol, acetone and methanol, and lithium source and dispersant are by every 1mol lithium sources are scattered in the ratio mixing in 0.1-10L dispersants.
It is preferred that, above-mentioned steps 8) M metal salts be zinc salt, magnesium salts, titanium salt, zirconates and vanadic salts in one or more.
It is rich present invention simultaneously provides modification lithium-ion battery stratiform is mixed with by one kind made from above-mentioned preparation method Nickel positive electrode, the chemical formula of lithium ion battery nickel-rich positive pole material is LiNi1-a-b-c-dCoaMnbAlcMdO2, wherein, a, b, c, D, x are molal quantity, 0<A≤0.3,0<B≤0.2,0<C≤0.05,0<D≤0.05 and 0<A+b+c+d≤0.5, M is metal ion One or more in Zn, Mg, Ti, Zr and V, MOxFor surface modification layer material, 1≤x≤3.
It is preferred that, above-mentioned surface modification layer material MOxWith lithium ion battery stratiform nickel-rich positive pole material LiNi1-a-b-c- dCoaMnbAlcMdO2Mass ratio be (0.0005-0.20)：1.
Compared with prior art, the invention has the advantages that and technique effect：
1st, the present invention is prepared by simple precursor doped, high temperature solid-phase sintering and the surface coated method of liquid phase One kind is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material.Metal M ion can improve the electronic conduction of material Property, while strengthening lithium ion conducting ability, advantageously in the deintercalation of lithium ion, stratiform nickel-rich positive pole material can be greatly improved High rate performance, and then improve the power density and energy density of anode material for lithium-ion batteries.MOxFinishing coat can reduce material The direct contact of material and electrolyte, reduction material absorb H2O/CO2The generation of side reaction is reduced with material surface alkali content, from And its cyclical stability and security performance are improved, the particularly long-term cycle performance of high temperature.
2nd, the raw material of preparation method of the present invention are easy to get, and process is simple, easy control of structure, and reappearance is high, can meet lithium ion The various needs of battery practical application, can realize industrialization large-scale production.
Brief description of the drawings
With reference to accompanying drawing, the invention will be further described, but the content in accompanying drawing is not construed as limiting the invention.
Fig. 1 is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material ZnO for gained in the embodiment of the present invention 2 LiNi0.63Co0.2Mn0.1Al0.05Zn0.02O2With pure phase nickel-rich positive pole material LiNi in comparative example0.65Co0.2Mn0.1Al0.05O2's XRD.
Fig. 2 is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material ZnO for gained in the embodiment of the present invention 2 LiNi0.63Co0.2Mn0.1Al0.05Zn0.02O2SEM figure.
Fig. 3 is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material ZnO for gained in the embodiment of the present invention 2 LiNi0.63Co0.2Mn0.1Al0.05Zn0.02O2With pure phase nickel-rich positive pole material LiNi in comparative example0.65Co0.2Mn0.1Al0.05O2 Charging and discharging curve compares figure within one week.
Fig. 4 is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material ZnO for gained in the embodiment of the present invention 2 LiNi0.63Co0.2Mn0.1Al0.05Zn0.02O2With pure phase nickel-rich positive pole material LiNi in comparative example0.65Co0.2Mn0.1Al0.05O2Times Rate performance curve ratio is relatively schemed.
Fig. 5 is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material ZnO for gained in the embodiment of the present invention 2 LiNi0.63Co0.2Mn0.1Al0.05Zn0.02O2With pure phase nickel-rich positive pole material LiNi in comparative example0.65Co0.2Mn0.1Al0.05O2Follow Ring performance curve compares figure.
Fig. 6 is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material ZnO for gained in the embodiment of the present invention 2 LiNi0.63Co0.2Mn0.1Al0.05Zn0.02O2With pure phase nickel-rich positive pole material LiNi in comparative example0.65Co0.2Mn0.1Al0.05O255 High temperature first charge-discharge curve ratio is relatively schemed at DEG C.
Embodiment
The invention will be further described in conjunction with specific embodiments, but the invention is not limited in these embodiments.
Embodiment 1.
A kind of preparation method for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, comprises the following steps：
1) nickel salt, cobalt salt, manganese salt, aluminium salt and M metal salts are weighed to be dissolved separately in deionized water, concentration is configured to respectively It is 0.05-2mol/L salting liquid；Nickel salt, cobalt salt, manganese salt, aluminium salt and M metal salts are according to before nickelic layered cathode material Drive body chemical formula Ni1-a-b-c-dCoaMnbAlcMd(OH)2The mol ratio of middle Ni, Co, Mn, Al and M element is weighed, wherein a, b, c, d, X is molal quantity, 0<A≤0.3,0<B≤0.2,0<C≤0.05,0<D≤0.05 and 0<A+b+c+d≤0.5, M is metal ion One or more in Zn, Mg, Ti, Zr and V.
Wherein, nickel salt is the one or more in nickel sulfate, nickel nitrate, nickel chloride, nickel oxalate and nickel acetate.Cobalt salt is sulphur One or more in sour cobalt, cobalt nitrate, cobalt chloride, cobalt oxalate and cobalt acetate.Manganese salt be manganese sulfate, manganese nitrate, manganese chloride and One or more in manganese acetate；Aluminium salt is the one or more in aluminum sulfate, aluminum nitrate and aluminium chloride；M metal salts be zinc salt, One or more in magnesium salts, titanium salt, zirconates or vanadic salts.
2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration For 0.2-2mol/L, the molar concentration of ammoniacal liquor is 0.1-1mol/L.Alkaline solution is sodium hydroxide solution and potassium hydroxide solution One or both of；When alkaline solution is sodium hydroxide solution, the mol ratio of sodium hydroxide and ammoniacal liquor is 2：1.
3) by step 2) gained mixed ammonium/alkali solutions be added in reactor, the volume of mixed ammonium/alkali solutions accounts for reactor volume %-80%, and control the pH value of liquid in reactor between 8-12, temperature is between 40-80 DEG C.
4) by step 1) nickel salt, cobalt salt, manganese salt, aluminium salt and the M metal salt solutions that prepare by peristaltic pump respectively at the uniform velocity Add in reactor, control the pH value of liquid in reactor between 8-12 in whole process, temperature is between 40-80 DEG C.
5) treat that nickel salt, cobalt salt, manganese salt, aluminium salt and M metal salts are added completely into, it is still aging 8-24 hours after, then will be heavy Form sediment and filter, wash, drying.
6) by step 5) obtain presoma Ni1-a-b-c-dCoaMnbAlcMd(OH)2It is well mixed with lithium source, lithium source, The mol ratio of presoma metal ion is Li：(Ni+Co+Mn+Al+M)=(1-1.1):1, lithium source be lithium hydroxide, lithium oxalate, One or more in lithium carbonate, lithium acetate and lithium nitrate.Then material is put into tube furnace, in 300- under oxygen atmosphere 600 DEG C are heated 3-10 hours, are then sintered 10-25 hours at 700-1000 DEG C, are naturally cooled to room temperature, produce M metals The lithium ion battery stratiform nickel-rich positive pole material LiNi of ion doping1-a-b-c-dCoaMnbAlcMdO2。
7) by the LiNi after doping1-a-b-c-dCoaMnbAlcMdO2Positive electrode is added in dispersant solution, ultrasonically treated 0.5-1 hours.Wherein, dispersant can be one kind in ethanol, acetone and methanol, and lithium source presses every 1mol lithium sources point with dispersant Dissipate the ratio mixing in 0.1-10L dispersants.
8) and then M metal salts are weighed add in deionized water and be made into M metal salt solutions, M metal salt solutions concentration is 0.1- 3mol/L.Wherein, M metal salts are the one or more in zinc salt, magnesium salts, titanium salt, zirconates and vanadic salts.By the M metals configured Salting liquid is added drop-wise to step 7) solution in, the solvent evaporated at 80-100 DEG C, at 100-120 DEG C dry 8-20 hours, so After crush, then sintered 1-8 hour under 300 DEG C -600 DEG C of air atmosphere, that is, obtain being mixed with modification lithium-ion battery layer Shape nickel-rich positive pole material MOx·LiNi1-a-b-c-dCoaMnbAlcMdO2.Surface modification layer material MOxIt is rich with lithium ion battery stratiform Nickel positive electrode LiNi1-a-b-c-dCoaMnbAlcMdO2Mass ratio be (0.0005-0.20)：1.
The present invention is prepared by simple precursor doped, high temperature solid-phase sintering and the surface coated method of liquid phase One kind is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material.Metal M ion can improve the electron conduction of material, Strengthen lithium ion conducting ability simultaneously, advantageously in the deintercalation of lithium ion, times of stratiform nickel-rich positive pole material can be greatly improved Rate performance, and then improve the power density and energy density of anode material for lithium-ion batteries.MOxFinishing coat can reduce material Direct contact, reduction material with electrolyte absorb H2O/CO2The generation of side reaction is reduced with material surface alkali content, so that Improve the long-term cycle performance of its cyclical stability and security performance, particularly high temperature.In addition, the former material of the preparation method of the present invention Material is easy to get, and process is simple, easy control of structure, and reappearance is high, can meet the various needs of lithium ion battery practical application, can realize Industrialization large-scale production.
Embodiment 2.
A kind of preparation method for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, comprises the following steps：
(1) according to stratiform nickel-rich positive pole material presoma chemical formula Ni0.63Co0.2Mn0.1Al0.05Zn0.02(OH)2Shown in Ni：Co：Mn：Al：Zn=0.63:0.2:0.1:0.05:0.02 mol ratio weighs 0.63mol nickel sulfates, 0.2mol sulphur respectively Sour cobalt, 0.1mol manganese sulfates, 0.025mol aluminum sulfate and the dissolving of 0.02mol zinc sulfate in deionized water, are configured to dense respectively Spend the salting liquid for 0.1mol/L；
(2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration For 0.2mol/L, the molar concentration of ammoniacal liquor is 0.1mol/L；
(3) by step 2) gained mixed ammonium/alkali solutions be added in reactor, the volume of mixed ammonium/alkali solutions accounts for reactor volume 50%, and control ph in 9, temperature control at 50 DEG C；
(4) by step 1) nickel sulfate, cobaltous sulfate, manganese sulfate, aluminum sulfate and the solution of zinc sulfate that prepare pass through peristaltic pump At the uniform velocity add respectively in reactor, the pH value in whole process is in 9, temperature control at 50 DEG C；
(5) nickel sulfate, cobaltous sulfate, manganese sulfate, aluminum sulfate and solution of zinc sulfate are added completely into, after still aging 12 hours, Then by precipitation filtering, washing, drying；
(6) 0.52mol lithium carbonates are weighed and are mixed with the material prepared in above-mentioned steps (1), tabletting is put into tubular type In stove, 500 DEG C are heated 5 hours under oxygen atmosphere, are then proceeded to be warming up to 850 DEG C and are sintered 15 hours, naturally cool to Room temperature, produces LiNi after doping0.63Co0.2Mn0.1Al0.05Zn0.02O2Stratiform nickel-rich positive pole material；
(7) by the LiNi after doping0.63Co0.2Mn0.1Al0.05Zn0.02O2Powder is added in ethanol solution, and ultrasonically treated 1 Hour；
(8) then weigh zinc nitrate 0.02mol add deionized water in be made into zinc nitrate solution, concentration is 1mol/L；Will The zinc nitrate solution configured is added drop-wise to step 7) solution in, the solvent evaporated at 100 DEG C, at 120 DEG C dry 10 hours, It is broken, sintered 5 hours under 400 DEG C of air atmosphere, that is, obtain being mixed with the rich nickel positive pole of modified lithium ion battery stratiform Material ZnOLiNi0.63Co0.2Mn0.1Al0.05Zn0.02O2。
In order to be contrasted to result, there is provided a comparative example.
Comparative example 1.
LiNi0.65Co0.2Mn0.1Al0.05O2Stratiform nickel-rich positive pole material, preparation technology is as follows：
(1) according to stratiform nickel-rich positive pole material presoma chemical formula Ni0.65Co0.2Mn0.1Al0.05(OH)2Shown in Ni：Co： Mn：Al=0.65:0.2:0.1:0.05 mol ratio weighs 0.65mol nickel sulfates, 0.2mol cobaltous sulfates, 0.1mol sulfuric acid respectively Manganese and the dissolving of 0.05mol aluminum sulfate in deionized water, are configured to the salting liquid that concentration is 0.1mol/L respectively；
(2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration For 0.2mol/L, the molar concentration of ammoniacal liquor is 0.1mol/L；
(3) mixed ammonium/alkali solutions obtained by step (2) are added in reactor, the volume of mixed ammonium/alkali solutions accounts for reactor volume 50%, and control ph is between 9, temperature is between 50 DEG C；
(4) nickel sulfate, cobaltous sulfate, manganese sulfate and the aluminum sulfate solution for preparing step (1) distinguish even by peristaltic pump Speed is added in reactor, and the pH value in whole process is between 9, temperature is between 50 DEG C；
(5) nickel sulfate, cobaltous sulfate, manganese sulfate and aluminum sulfate solution are added completely into, after still aging 12 hours, then will be heavy Form sediment and filter, wash, drying；
(6) 1.05mol lithium hydroxides are weighed and are mixed with the material prepared in above-mentioned steps (1), tabletting is put into pipe In formula stove, 500 DEG C are heated 5 hours under oxygen atmosphere, are then proceeded to be warming up to 850 DEG C and are sintered 15 hours, natural cooling To room temperature, LiNi is produced0.65Co0.2Mn0.1Al0.05O2Stratiform nickel-rich positive pole material.
According to Fig. 1 X-ray powder diffraction (XRD) analysis result, the LiNi of comparative example 10.65Co0.2Mn0.1Al0.05O2Layer Shape nickel-rich positive pole material products therefrom has good layer structure, and crystallinity is high.Embodiment 1 is mixed with modified lithium ion Battery stratiform nickel-rich positive pole material ZnOLiNi0.63Co0.2Mn0.1Al0.05Zn0.02O2Products therefrom has good layer structure, Crystallinity is high, also demonstrates to be mixed with and is changed without result in lithium ion battery stratiform nickel-rich positive pole material structure.
From Fig. 2 SEM (SEM) it can be seen from the figure that, being mixed with material modified for embodiment 1 is two The high compact of secondary particle packing is spherical, and particle diameter is 12-14 microns.
As shown in figure 3, the material of comparative example 1 is at 25 DEG C, carrying out discharge and recharge between 2.0-4.3V with 0.1C multiplying power follows During ring, lithium ion battery stratiform nickel-rich positive pole material pure phase LiNi0.65Co0.2Mn0.1Al0.05O2Discharge capacity first be 178.4mAh/g.At 25 DEG C, when carrying out charge and discharge cycles between 2.0-4.3V with 0.1C multiplying power, lithium ion battery stratiform is rich Nickel positive electrode ZnOLiNi0.63Co0.2Mn0.1Al0.05Zn0.02O2Discharge capacity first be 207.6mAh/g.Embodiment 1 Performance is better than the performance of comparative example 1.
As shown in figure 4, at 25 DEG C, with 1C, 2C, 5C, the big multiplying power such as 10C carries out charge-discharge test, the material of comparative example 1 Specific discharge capacity is respectively 168.3mAh/g, 158.4mAh/g, 139.2mAh/g, 120.1mAh/g.At 25 DEG C, with 1C, 2C, 5C, 10C etc. are big, and multiplying power carries out charge-discharge test, and the material discharging specific capacity of embodiment 1 is respectively 176.4mAh/g, 143.2mAh/g, 129.2mAh/g, 110.0mAh/g.
As shown in figure 5, at 25 DEG C, with discharge and recharge under 1C multiplying powers, the material of the comparative example 1 after circulating 200 weeks is reversible to be held Measure as 123.0mAh/g.At 25 DEG C, with discharge and recharge under 1C multiplying powers, the reversible capacity of the embodiment 1 after circulating 200 weeks is 153.0mAh/g。
As shown in fig. 6, at 55 DEG C, initial charge capacity is 231.9mAh/g under 0.1C multiplying powers, discharge capacity is The discharge capacity of the material of comparative example 1 is 151.8mAh/g under 1C multiplying powers after 189.4mAh/g, the circle of circulation 100.At 55 DEG C, Initial charge capacity is 281.9mAh/g under 0.1C multiplying powers, and discharge capacity is 236.4mAh/g, after the circle of circulation 100 under 1C multiplying powers The discharge capacity of the material of embodiment 1 is 169.8mAh/g, it is shown that excellent chemical property.
In summary, the modification lithium-ion battery stratiform nickel-rich positive pole material manufactured in the present embodiment that is mixed with can be carried significantly The high rate performance of high stratiform nickel-rich positive pole material, and then the power density and energy density of improvement anode material for lithium-ion batteries, The cyclical stability and security performance of material, the particularly long-term cycle performance of high temperature can be improved.In addition, the preparation side of the present invention The raw material of method are easy to get, and process is simple, easy control of structure, and reappearance is high, can meet the various needs of lithium ion battery practical application, Industrialization large-scale production can be realized.
Embodiment 3：
A kind of preparation method for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, comprises the following steps：
(1) according to stratiform nickel-rich positive pole material presoma chemical formula Ni0.74Co0.1Mn0.1Al0.04Mg0.02(OH)2Shown in Ni：Co：Mn：Al：Mg=0.74:0.1:0.1:0.04:0.02 mol ratio weighs 1.48mol nickel nitrates, 0.2mol nitre respectively Sour cobalt, 0.2mol manganese nitrates, 0.08mol aluminum nitrates and the dissolving of 0.04mol magnesium nitrates in deionized water, are configured to concentration respectively For 0.2mol/L salting liquid；
(2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration For 0.4mol/L, the molar concentration of ammoniacal liquor is 0.2mol/L；
(3) mixed ammonium/alkali solutions obtained by step (2) are added in reactor, the volume of mixed ammonium/alkali solutions accounts for reactor volume 40%, and control ph in 8, temperature control at 40 DEG C；
(4) nickel nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate and the magnesium nitrate solution for preparing step (1) pass through peristaltic pump At the uniform velocity add respectively in reactor, the pH value in whole process is in 8, temperature control at 40 DEG C；
(5) nickel nitrate, cobalt nitrate, manganese nitrate, aluminum nitrate and magnesium nitrate solution are added completely into, after still aging 8 hours, so Afterwards by precipitation filtering, washing, drying；
(6) 2.1mol lithium nitrates are weighed and are mixed with the material prepared in above-mentioned steps (1), tabletting is put into tubular type In stove, 500 DEG C are heated 3 hours under oxygen atmosphere, are then proceeded to be warming up to 800 DEG C and are sintered 10 hours, naturally cool to Room temperature, produces LiNi after doping0.74Co0.1Mn0.1Al0.04Mg0.02O2Stratiform nickel-rich positive pole material.
(7) by the LiNi after doping0.74Co0.1Mn0.1Al0.04Mg0.02O2Powder is added in acetone soln, and ultrasound 1 is small When；
(8) then weigh magnesium nitrate 0.05mol add deionized water in be made into magnesium nitrate solution, concentration is 0.5mol/L； In the solution that the magnesium nitrate solution configured is added drop-wise to step (7), the solvent evaporated at 80 DEG C dries 8 small at 100 DEG C When, crush, sintered 2 hours under 300 DEG C of air atmosphere, that is, obtain being mixed with the rich nickel of modified lithium ion battery stratiform just Pole material MgOLiNi0.74Co0.1Mn0.1Al0.04Mg0.02O2。
There is good layer structure by X-ray powder diffraction (XRD) analysis shows products therefrom, crystallinity is high.Scanning It is the spherical of second particle accumulation that electron microscope (SEM) it can be seen from the figure that, which is mixed with material modified, and particle diameter is 12-16 Micron.At 25 DEG C, when carrying out charge and discharge cycles between 2.0-4.3V with 0.1C multiplying power, lithium ion battery stratiform richness nickel positive pole Material MgOLiNi0.74Co0.1Mn0.1Al0.04Mg0.02O2Discharge capacity first be 193.6mAh/g.At 25 DEG C, with 1C, The big multiplying power such as 2C, 5C, 10C carries out charge-discharge test, and its specific discharge capacity is respectively 170.8mAh/g, 163.8mAh/g, 158.2mAh/g, 149.0mAh/g.At 25 DEG C, with discharge and recharge under 1C multiplying powers, its reversible capacity after circulating 200 weeks is 151.9mAh/g.At 55 DEG C, initial charge capacity is 238.8mAh/g under 0.1C multiplying powers, and discharge capacity is 201.4mAh/g, Circulation 100 circle after 1C multiplying powers discharge capacity be 161.8mAh/g, it is shown that excellent chemical property.
In summary, the modification lithium-ion battery stratiform nickel-rich positive pole material manufactured in the present embodiment that is mixed with can be carried significantly The high rate performance of high stratiform nickel-rich positive pole material, and then the power density and energy density of improvement anode material for lithium-ion batteries, The cyclical stability and security performance of material, the particularly long-term cycle performance of high temperature can be improved.In addition, the preparation side of the present invention The raw material of method are easy to get, and process is simple, easy control of structure, and reappearance is high, can meet the various needs of lithium ion battery practical application, Industrialization large-scale production can be realized.
Embodiment 4.
A kind of preparation method for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, comprises the following steps：
(1) according to stratiform nickel-rich positive pole material presoma chemical formula Ni0.83Co0.05Mn0.07Al0.04Ti0.01(OH)2Shown in Ni：Co：Mn：Al：Zn=0.83:0.05:0.07:0.04:0.01 mol ratio weighs 0.83mol nickel chlorides, 0.05mol respectively Cobalt chloride, 0.07mol manganese chlorides, 0.04mol aluminium chloride and the dissolving of 0.01mol butyl titanates in deionized water, are prepared respectively Into the salting liquid that concentration is 0.1mol/L；
(2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration For 1mol/L, the molar concentration of ammoniacal liquor is 0.5mol/L；
(3) by step 2) gained mixed ammonium/alkali solutions be added in reactor, the volume of mixed ammonium/alkali solutions accounts for reactor volume 60%, and control ph in 10, temperature control at 60 DEG C；
(4) by step 1) nickel chloride, cobalt chloride, manganese chloride, aluminium chloride and the butyl titanate solution that prepare passes through and wriggles Pump is at the uniform velocity added in reactor respectively, and the pH value in whole process is in 10, temperature control at 60 DEG C；
(5) nickel chloride, cobalt chloride, manganese chloride, aluminium chloride and butyl titanate solution are added completely into, still aging 12 hours Afterwards, then by precipitation filtering, washing, drying；
(6) 1.08mol lithium hydroxides are weighed and are mixed with the material prepared in above-mentioned steps (1), tabletting is put into pipe In formula stove, 550 DEG C are heated 6 hours under oxygen atmosphere, are then proceeded to be warming up to 750 DEG C and are sintered 12 hours, natural cooling To room temperature, LiNi after doping is produced0.83Co0.05Mn0.07Al0.04Ti0.01O2Stratiform nickel-rich positive pole material.
(7) by the LiNi after doping0.83Co0.05Mn0.07Al0.04Ti0.01O2Powder is added in methanol solution, and ultrasound 1 is small When；
(8) then weigh titanium tetrachloride 0.02mol add deionized water in be made into titanium tetrachloride solution, concentration is 1mol/ L；The titanium tetrachloride solution configured is added drop-wise to step 7) solution in, the solvent evaporated at 90 DEG C, at 110 DEG C dry 12 Hour, crush, sintered 6 hours under 450 DEG C of air atmosphere, that is, obtain being mixed with the rich nickel of modified lithium ion battery stratiform Positive electrode TiO2·LiNi0.83Co0.05Mn0.07Al0.04Ti0.01O2。
X-ray powder diffraction (XRD) analysis shows products therefrom has good layer structure, and crystallinity is high.Scanning electron Microscope (SEM) it can be seen from the figure that be mixed with it is material modified be second particle be piled into it is spherical, particle diameter be 8-12 it is micro- Rice.
At 25 DEG C, when carrying out charge and discharge cycles between 2.0-4.3V with 0.1C multiplying power, lithium ion battery stratiform richness nickel Positive electrode TiO2·LiNi0.83Co0.05Mn0.07Al0.04Ti0.01O2Discharge capacity first be 204.4mAh/g.At 25 DEG C, With 1C, 2C, 5C, the big multiplying power such as 10C carry out charge-discharge test, and its specific discharge capacity is respectively 183.1mAh/g, 176.2mAh/g, 163.1mAh/g, 154.9mAh/g.At 25 DEG C, with discharge and recharge under 1C multiplying powers, its reversible capacity after circulating 200 weeks is 169.0mAh/g.At 55 DEG C, initial charge capacity is 253.1mAh/g under 0.1C multiplying powers, and discharge capacity is 211.0mAh/g, Circulation 100 circle after 1C multiplying powers discharge capacity be 165.5mAh/g, it is shown that excellent chemical property.
In summary, the modification lithium-ion battery stratiform nickel-rich positive pole material manufactured in the present embodiment that is mixed with can be carried significantly The high rate performance of high stratiform nickel-rich positive pole material, and then the power density and energy density of improvement anode material for lithium-ion batteries, The cyclical stability and security performance of material, the particularly long-term cycle performance of high temperature can be improved.In addition, the preparation side of the present invention The raw material of method are easy to get, and process is simple, easy control of structure, and reappearance is high, can meet the various needs of lithium ion battery practical application, Industrialization large-scale production can be realized.
Embodiment 5.
(1) according to stratiform nickel-rich positive pole material presoma chemical formula Ni0.90Co0.04Mn0.03Al0.025V0.005(OH)2Shown in Ni：Co：Mn：Al：Zn=0.9:0.04:0.03:0.025:0.005 mol ratio weighs 0.9mol nickel oxalates, 0.04mol respectively Cobalt oxalate, 0.03mol manganese oxalates, 0.025mol aluminium chloride and the dissolving of 0.005mol ammonium metavanadates in deionized water, are matched somebody with somebody respectively The salting liquid that concentration is 0.15mol/L is made；
(2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration For 1.6mol/L, the molar concentration of ammoniacal liquor is 0.8mol/L；
(3) by step 2) gained mixed ammonium/alkali solutions be added in reactor, the volume of mixed ammonium/alkali solutions accounts for reactor volume 70%, and control ph in 11, temperature control at 70 DEG C；
(4) by step 1) nickel oxalate, cobalt oxalate, manganese oxalate, aluminium chloride and the ammonium metavanadate solution that prepare pass through and wriggle Pump is at the uniform velocity added in reactor respectively, and the pH value in whole process is in 11, temperature control at 70 DEG C；
(5) nickel oxalate, cobalt oxalate, manganese oxalate, aluminium chloride and ammonium metavanadate solution are added completely into, still aging 16 hours Afterwards, then by precipitation filtering, washing, drying；
(6) 1.1mol lithium acetates are weighed and are mixed with the material prepared in above-mentioned steps (1), tabletting is put into tubular type In stove, 400 DEG C are heated 8 hours under oxygen atmosphere, are then proceeded to be warming up to 700 DEG C and are sintered 10 hours, naturally cool to Room temperature, produces LiNi after doping0.90Co0.04Mn0.03Al0.025V0.005O2Stratiform nickel-rich positive pole material；
(7) by the LiNi after doping0.90Co0.04Mn0.03Al0.025V0.005O2Powder is added in ethanol solution, and ultrasound 1 is small When；
(8) then weigh zinc nitrate 0.02mol add deionized water in be made into zinc nitrate solution, concentration is 1mol/L；Will The zinc nitrate solution configured is added drop-wise to step 7) solution in, the solvent evaporated at 100 DEG C, at 120 DEG C dry 10 hours, It is broken, sintered 5 hours under 400 DEG C of air atmosphere, that is, obtain being mixed with the rich nickel positive pole of modified lithium ion battery stratiform Material VO2.5·LiNi0.90Co0.04Mn0.03Al0.025V0.005O2。
X-ray powder diffraction (XRD) analysis shows products therefrom has good layer structure, and crystallinity is high.Scanning electron It is that high compact is spherical that microscope (SEM) it can be seen from the figure that, which is mixed with material modified, and particle diameter is 12-16 microns.
At 25 DEG C, when carrying out charge and discharge cycles between 2.0-4.3V with 0.1C multiplying power, lithium ion battery stratiform richness nickel Positive electrode VO2.5·LiNi0.90Co0.04Mn0.03Al0.025V0.005O2Discharge capacity first be 208.6mAh/g.At 25 DEG C, With 1C, 2C, 5C, the big multiplying power such as 10C carry out charge-discharge test, and its specific discharge capacity is respectively 191.3mAh/g, 180.4mAh/g, 161.4mAh/g, 150.8mAh/g.At 25 DEG C, with discharge and recharge under 1C multiplying powers, its reversible capacity after circulating 200 weeks is 169.0mAh/g.At 55 DEG C, initial charge capacity is 255.9mAh/g under 0.1C multiplying powers, and discharge capacity is 212.4mAh/g, Circulation 100 circle after 1C multiplying powers discharge capacity be 154.8mAh/g, it is shown that excellent chemical property.
In summary, the modification lithium-ion battery stratiform nickel-rich positive pole material manufactured in the present embodiment that is mixed with can be carried significantly The high rate performance of high stratiform nickel-rich positive pole material, and then the power density and energy density of improvement anode material for lithium-ion batteries, The cyclical stability and security performance of material, the particularly long-term cycle performance of high temperature can be improved.In addition, the preparation side of the present invention The raw material of method are easy to get, and process is simple, easy control of structure, and reappearance is high, can meet the various needs of lithium ion battery practical application, Industrialization large-scale production can be realized.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected The limitation of scope, although being explained in detail with reference to preferred embodiment to the present invention, one of ordinary skill in the art should manage Solution, technical scheme can be modified or equivalent substitution, without departing from technical solution of the present invention essence and Scope.

Claims (10)

1. a kind of preparation method for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, it is characterised in that including with Lower step：
1) weigh nickel salt, cobalt salt, manganese salt, aluminium salt and M metal salts to be dissolved separately in deionized water, concentration is configured to respectively is 0.05-2mol/L salting liquid；The nickel salt, cobalt salt, manganese salt, aluminium salt and M metal salts are according to before nickelic layered cathode material Drive body chemical formula Ni1-a-b-c-dCoaMnbAlcMd(OH)2The mol ratio of middle Ni, Co, Mn, Al and M element is weighed, wherein a, b, c, d, X is molal quantity, 0<A≤0.3,0<B≤0.2,0<C≤0.05,0<D≤0.05 and 0<A+b+c+d≤0.5, M is metal ion One or more in Zn, Mg, Ti, Zr and V；
2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration is 0.2-2mol/L, the molar concentration of ammoniacal liquor is 0.1-1mol/L；
3) by step 2) gained mixed ammonium/alkali solutions be added in reactor, the volume of mixed ammonium/alkali solutions accounts for the %- of reactor volume 80%, and control the pH value of liquid in reactor between 8-12, temperature is between 40-80 DEG C；
4) by step 1) nickel salt, cobalt salt, manganese salt, aluminium salt and the M metal salt solutions that prepare at the uniform velocity added respectively by peristaltic pump In reactor, control the pH value of liquid in reactor between 8-12 in whole process, temperature is between 40-80 DEG C；
5) treat that nickel salt, cobalt salt, manganese salt, aluminium salt and M metal salts are added completely into, it is still aging 8-24 hours after, then will precipitate Filter, washing, drying；
6) by step 5) obtain presoma Ni1-a-b-c-dCoaMnbAlcMd(OH)2It is well mixed with lithium source, lithium source, forerunner The mol ratio of body metal ion is Li：(Ni+Co+Mn+Al+M)=(1-1.1):1；Then material is put into tube furnace, in oxygen Atmosphere heats 3-10 hours under enclosing in 300-600 DEG C, then sinters 10-25 hours, naturally cools at 700-1000 DEG C Room temperature, produces the lithium ion battery stratiform nickel-rich positive pole material LiNi of M metal ion mixings1-a-b-c-dCoaMnbAlcMdO2；
7) by the LiNi after doping1-a-b-c-dCoaMnbAlcMdO2Positive electrode is added in dispersant solution, ultrasonically treated 0.5-1 Hour；
8) and then M metal salts are weighed add in deionized water and be made into M metal salt solutions, M metal salt solutions concentration is 0.1-3mol/ L；
The M metal salt solutions configured are added drop-wise to step 7) solution in, the solvent evaporated at 80-100 DEG C, in 100-120 Dry 8-20 hours, then crush at DEG C, then sintered 1-8 hours under 300 DEG C -600 DEG C of air atmosphere, that is, obtain doping bag Cover modification lithium-ion battery stratiform nickel-rich positive pole material MOx·LiNi1-a-b-c-dCoaMnbAlcMdO2。
2. the preparation method according to claim 1 for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, its It is characterised by, the nickel salt is the one or more in nickel sulfate, nickel nitrate, nickel chloride, nickel oxalate and nickel acetate.
3. the preparation method according to claim 1 for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, its It is characterised by, the cobalt salt is the one or more in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt oxalate and cobalt acetate.
4. the preparation method according to claim 1 for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, its It is characterised by, the manganese salt is the one or more in manganese sulfate, manganese nitrate, manganese chloride and manganese acetate；Aluminium salt is aluminum sulfate, nitre One or more in sour aluminium and aluminium chloride；M metal salts are the one or more in zinc salt, magnesium salts, titanium salt, zirconates or vanadic salts.
5. the preparation method according to claim 1 for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, its Be characterised by, step 2) described in alkaline solution be one or both of sodium hydroxide solution and potassium hydroxide solution；Work as alkali Property solution when being sodium hydroxide solution, the mol ratio of sodium hydroxide and ammoniacal liquor is 2：1.
6. the preparation method according to claim 1 for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, its Be characterised by, step 6) lithium source be lithium hydroxide, lithium oxalate, lithium carbonate, lithium acetate and lithium nitrate in one or more.
7. the preparation method according to claim 1 for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, its Be characterised by, step 7) dispersant be one kind in ethanol, acetone and methanol, and lithium source and dispersant are pressed per 1mol lithium sources point Dissipate the ratio mixing in 0.1-10L dispersants.
8. the preparation method according to claim 1 for being mixed with modification lithium-ion battery stratiform nickel-rich positive pole material, its Be characterised by, step 8) M metal salts be zinc salt, magnesium salts, titanium salt, zirconates and vanadic salts in one or more.
9. one kind made from the preparation method according to claim any one of 1-8 is mixed with modification lithium-ion battery stratiform Nickel-rich positive pole material, it is characterised in that the chemical formula of the lithium ion battery nickel-rich positive pole material is LiNi1-a-b-c- dCoaMnbAlcMdO2, wherein, a, b, c, d, x are molal quantity, 0<A≤0.3,0<B≤0.2,0<C≤0.05,0<D≤0.05 and 0< A+b+c+d≤0.5, M is the one or more in configuration metal ions Zn, Mg, Ti, Zr and V, MOxFor surface modification layer material, 1≤x ≤3。
10. it is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material according to described in claim 9, it is characterised in that institute State surface modification layer material MOxWith lithium ion battery stratiform nickel-rich positive pole material LiNi1-a-b-c-dCoaMnbAlcMdO2Mass ratio For (0.0005-0.20)：1.
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