CN107093741B - A kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material - Google Patents

A kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material Download PDF

Info

Publication number
CN107093741B
CN107093741B CN201710389952.0A CN201710389952A CN107093741B CN 107093741 B CN107093741 B CN 107093741B CN 201710389952 A CN201710389952 A CN 201710389952A CN 107093741 B CN107093741 B CN 107093741B
Authority
CN
China
Prior art keywords
nickel cobalt
lithium aluminate
lithium
cobalt lithium
aluminate cathode
Prior art date
Application number
CN201710389952.0A
Other languages
Chinese (zh)
Other versions
CN107093741A (en
Inventor
张锁江
刘艳侠
马立彬
刘凡
张若涛
陈昊
Original Assignee
郑州中科新兴产业技术研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to CN201710384793 priority Critical
Priority to CN2017103847935 priority
Application filed by 郑州中科新兴产业技术研究院 filed Critical 郑州中科新兴产业技术研究院
Publication of CN107093741A publication Critical patent/CN107093741A/en
Application granted granted Critical
Publication of CN107093741B publication Critical patent/CN107093741B/en

Links

Classifications

    • H—ELECTRICITY
    • H01—BASIC 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—BASIC 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—BASIC 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—BASIC 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—BASIC 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • 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 kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material, it the following steps are included: (1) nickel cobalt lithium aluminate presoma preparation；(2) the lithium position doping vario-property of potassium ion；(3) lithium-containing compound clad is constructed.The present invention is replaced by the lithium position of potassium ion, is effectively improved the diffusion rate of lithium ion, is improved the high rate performance of material；The lithium-containing compound layer that material surface is constructed simultaneously can reduce material surface residual alkali content, reduce the flatulence of later period battery core；Effectively inhibit side reaction, promotes structural stability of the material in cyclic process；Lithium-containing compound layer has high conductive performance to lithium ion, accelerates the insertion and abjection of lithium ion, lithium-ion-conducting is poor when solving the problems, such as common metal oxides as clad, improves the cycle performance and high rate performance of material.

Description

A kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material

Technical field

The invention belongs to field of lithium ion battery anode, in particular to a kind of high magnification nickel cobalt lithium aluminate cathode material Preparation method.

Technical background

Lithium ion battery with its high-energy, the service life is long, pollution-free the advantages that, be widely used to mobile phone, laptop Equal fields, while also starting to be applied to the power batteries fields such as electric bicycle, electric car.Lithium cobaltate cathode material is earliest Realize commercialized positive electrode, but since cobalt resource is limited and expensive, pollution is big, limits its further development.It is high Nickel system positive electrode Li (NixM1-x)O2(x >=0.6) becomes important lithium-ion electric because cost is relatively low, capacity is high and environmental-friendly Pond positive electrode.As LiNiO2、LiCoO2And LiAlO2The class matter of three is the same as phase solid solution, nickel cobalt lithium aluminate (LiNi0.8Co0.15Al0.05O2, abbreviation NCA) and the advantages of being provided simultaneously with the above three, it is considered as the substitute of cobalt acid lithium, dynamic Power field of batteries will have boundless application market.

NCA material still remains some problems during battery applications: (1) due to cationic mixing effect and material The phase transformation for expecting surface micro-structure causes irreversible capacity loss and the cycle performance decline of NCA；(2) electricity of NCA material preparation It is more serious that core produces gas；(3) lithium ion diffusion coefficient is low, so that the high rate performance of material is less desirable.It is asked for above-mentioned these Topic can improve its chemical property by ion doping and surface cladding.

The doping vario-property of NCA material is studied at present, the ionic compartmentation of transition metal layer is substantially, although can be certain The chemical property of material is improved in degree, but the ionic compartmentation of transition metal layer cannot promote the migration rate of lithium ion.Such as Disclose nickel cobalt lithium aluminate cathode material and preparation method thereof application No. is 201410445867.8 invention, but it is disclosed just Pole material is the ionic compartmentation of transition metal layer, can stablize lattice structure, but cannot promote the migration rate of lithium ion.To NCA It is oxide/phosphate etc. that material, which carries out covering material used by surface coats, and clad hinders electrolyte to material Burn into inhibits the side reaction of material and electrolyte, but simultaneously as its electrochemicaUy inert, also can be to the biography of electronics and lithium ion It leads and causes to hinder.It is modified by alumina-coated respectively that such as application No. is 201410004698.4 inventions, due to these substances For electrochemically inactive material, the capacity of active material can be hindered to play.

Therefore a kind of novel nickel cobalt lithium aluminate cathode material, the Lai Gaishan above problem need to be developed, the invention patent passes through The modified method of lithium-containing compound clad is adulterated and constructed in the lithium position of potassium ion, improves the chemical property of NCA material.

Summary of the invention

The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of high magnification nickel cobalt lithium aluminate The preparation method of positive electrode.The present invention is adulterated by the lithium position of potassium ion, is increased the interlayer spacing of lithium layer, is promoted lithium ion Diffusion rate improves the high rate performance of material；It is (remained on surface relative to the difference of other positive electrodes for NCA material Alkaline matter is higher) characteristic, design can react with surface residual alkali, generate the clad containing lithium with electro-chemical activity, improvement The insertion and abjection of lithium ion finally improve the cycle performance and high rate performance of material.

In order to solve the above technical problems, the invention adopts the following technical scheme:

A kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material, steps are as follows:

(1) preparation of nickel cobalt lithium aluminate persursor material: by uniformly mixed nickel, cobalt salt solution, and dissolved with aluminium salt Ammonium hydroxide and sodium hydroxide mixed solution are injected in the reaction kettle containing bottom liquid simultaneously by certain speed, control entire reactant The pH of system is 9-12, and agitating and heating reacts 8-16 h, and the solution after reaction is done at 80-120 DEG C by ageing, washing, filtering It is dry, obtain nickel cobalt lithium aluminate persursor material；

(2) the lithium position doping vario-property of potassium ion: (herein by resulting nickel cobalt lithium aluminate persursor material and sylvite and lithium salts Persursor material and the molar ratio of sylvite or lithium salts please limit) mixed calcining, crushed 200 mesh screens, obtain doping vario-property Nickel cobalt lithium aluminate cathode material afterwards；

(3) lithium-containing compound clad is constructed: modifying agent being dissolved in dehydrated alcohol, is uniformly dispersed, be then added and mix Miscellaneous modified nickel cobalt lithium aluminate cathode material, is dried to obtain powder after being stirred to react 3-10 h under conditions of 50 ~ 100 DEG C, By calcining, it is cooled to room temperature, obtains high magnification nickel cobalt lithium aluminate cathode material.

Sylvite in the step (2) is potassium carbonate, carbonic acid potassium dihydrogen, bicarbonate dipotassium, potassium nitrate, potassium sulfate, acetic acid One or more of potassium.

The molar ratio of nickel cobalt lithium aluminate persursor material and lithium salts is 1:1 ~ 1.05, sylvite and lithium salts in the step (2) Molar ratio be 0.01 ~ 0.05:1.

Calcination temperature in the step (2) is 700 DEG C ~ 850 DEG C, and calcination time is 10 ~ 20 h.

Modifying agent in the step (3) is ammonium metavanadate, in ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, cobalt phosphate One or more.

The molar ratio of modifying agent and nickel cobalt lithium aluminate cathode material in the step (3) is 0.003 ~ 0.015:1.

Calcination temperature in the step (3) is 200 DEG C ~ 400 DEG C, and calcination time is 2 ~ 10h.

Beneficial effects of the present invention: the present invention is the modified method by adulterating and surface surrounding phase combines, out of material Portion and the external comprehensive performance for improving material: (1) the biggish potassium ion of ionic radius in the lithium layer of NCA material is introduced, was both pressed down It makes cationic mixing, stablize lattice structure, and the interlamellar spacing of lithium layer can be increased, promote the diffusion rate of lithium ion, improve NCA Cycle performance and high rate performance；(2) feature high for the surface NCA residual alkali content, design can react generation containing lithium with residual alkali Compound clad can both reduce the surface NCA residual alkali content, reduce the flatulence of later period battery core, and material can be promoted to recycle Structural stability in the process, and improve the insertion and abjection of lithium ion, the final cycle performance for promoting NCA material and forthright again Energy.

Detailed description of the invention

Fig. 1 is the scanning electron microscope (SEM) photograph of nickel cobalt lithium aluminate cathode material obtained in embodiment 1；

Fig. 2 is discharge curve of nickel cobalt lithium aluminate cathode material under the conditions of 0.2 C obtained in embodiment 1；

Fig. 3 is cycle performance figure of the nickel cobalt lithium aluminate cathode material under different multiplying obtained in embodiment 1.

Specific embodiment

The present invention will be described in detail combined with specific embodiments below.

Embodiment 1

The preparation method of the high magnification nickel cobalt lithium aluminate cathode material of the present embodiment, steps are as follows:

(1) preparation of nickel cobalt lithium aluminate presoma: 85:15 weighs nickel nitrate and cobalt nitrate crystals in molar ratio, is dissolved in water It is uniformly mixed obtained mixed solution A afterwards, concentration of metal ions is 1.0 mol/L, weighs 5mol aluminum nitrate and is dissolved in 2 mol/L ammonia Mixed solution B is made in the mixed solution of water and 4 mol/L sodium hydroxides, and mixed solution A and mixed solution B are injected simultaneously and contained In the reaction kettle of bottom liquid, the pH value of entire reaction system is controlled 11.0 ± 0.02, mixing speed is 500 r/min, reaction 12 H, temperature are 55 DEG C, and reaction product is dry at 120 DEG C after ageing, washing, filtering, obtain nickel cobalt lithium aluminate presoma Material；

(2) the lithium position doping vario-property of potassium ion: by resulting nickel cobalt lithium aluminate persursor material, lithium hydroxide and potassium nitrate After mixing under oxygen atmosphere 750 DEG C of 16 h of calcining, crushed 200 mesh screens, obtain the nickel cobalt lithium aluminate anode of doping vario-property Material；Wherein the molar ratio of nickel cobalt lithium aluminate persursor material and lithium hydroxide is 1:1.05, and potassium nitrate and lithium hydroxide rub You are than being 0.02:1；

(3) lithium-containing compound clad is constructed: that 0.05 g(0.00043 mol) ammonium metavanadate is dissolved in 60 mL is anhydrous In ethyl alcohol, it is uniformly dispersed, the 10.0 g(0.11 mol of nickel cobalt aluminic acid lithium material after doping vario-property is added in Xiang Shangshu solution), It is stirred to react 3 h under conditions of 100 DEG C, powder is dried to obtain at 100 DEG C, dry powder is crushed after cooling, obtained in 400 DEG C of 3 h of calcining To powerful nickel cobalt lithium aluminate cathode material.

The scanning electron microscope (SEM) photograph of nickel cobalt lithium aluminate cathode material is as shown in Figure 1.Products therefrom is assembled into button cell 2.8 Charge and discharge are carried out within the scope of ~ 4.3 V.Discharge curve of the nickel cobalt lithium aluminate cathode material that Fig. 2 is under the conditions of 0.2 C； Cycle performance figure of the nickel cobalt lithium aluminate cathode material that Fig. 3 is under different multiplying.Under the conditions of 0.2 C, gained nickel cobalt aluminium The specific discharge capacity of sour lithium anode material be 198 mAh/g, circulation 100 circle after, specific discharge capacity be 185 mAh/g, have compared with Good cycle performance and high rate performance.

Embodiment 2

The preparation method of the high magnification nickel cobalt lithium aluminate cathode material of the present embodiment, steps are as follows:

(1) preparation of nickel cobalt lithium aluminate presoma: 85:15 weighs nickel sulfate and cobaltous sulfate crystal in molar ratio, is dissolved in water After be uniformly mixed, concentration of metal ions is 1.0 mol/L, and the aluminum sulfate for weighing 5mol is dissolved in 2 mol/L ammonium hydroxide and 4 mol/L In the mixed solution of sodium hydroxide, two kinds of mixed solutions are injected in the reaction kettle containing bottom liquid simultaneously, control entire reactant For the pH value of system 11.5 ± 0.02, mixing speed is 700 r/min, reacts 16 h, and temperature is 50 DEG C, and reaction product is by old Change, wash, after filtering, it is dry at 100 DEG C, obtain nickel cobalt lithium aluminate persursor material；

(2) the lithium position doping vario-property of potassium ion: resulting nickel cobalt lithium aluminate persursor material, lithium carbonate and potassium carbonate are mixed After conjunction under oxygen atmosphere 800 DEG C of 10 h of calcining, crushed 200 mesh screens, obtain the nickel cobalt lithium aluminate anode material of doping vario-property Material；Wherein the molar ratio of nickel cobalt lithium aluminate persursor material and lithium carbonate is 1:1.02, and the molar ratio of potassium carbonate and lithium carbonate is 0.05:1；

(3) lithium-containing compound clad is constructed: that 0.2 g(0.0013 mol) ammonium dihydrogen phosphate is dissolved in 60 mL is anhydrous In ethyl alcohol, it is uniformly dispersed, the 10.0 g(0.11 mol of nickel cobalt aluminic acid lithium material after doping vario-property is added in Xiang Shangshu solution), It is stirred to react 5 h under conditions of 80 DEG C, powder is dried to obtain at 100 DEG C, dry powder is crushed after cooling, obtained in 300 DEG C of 10 h of calcining To powerful nickel cobalt lithium aluminate cathode material.

Under the conditions of 0.2 C, the specific discharge capacity of gained nickel cobalt lithium aluminate cathode material is 180 mAh/g, 100 circle of circulation Afterwards, specific discharge capacity is 165 mAh/g, has preferable cycle performance.

Embodiment 3

The preparation method of the high magnification nickel cobalt lithium aluminate cathode material of the present embodiment, steps are as follows:

(1) preparation of nickel cobalt lithium aluminate presoma: 85:15 weighs nickel nitrate and cobalt nitrate crystals in molar ratio, is dissolved in water After be uniformly mixed, concentration of metal ions is 5.0 mol/L, and the aluminum nitrate for weighing 5mol is dissolved in 10 mol/L ammonium hydroxide and 20 In the mixed solution of mol/L sodium hydroxide, two kinds of mixed solutions are injected in the reaction kettle containing bottom liquid simultaneously, control is entire anti- Answer the pH value of system 12.0 ± 0.02, mixing speed is 800 r/min, reacts 8 h, and temperature is 55 DEG C, and reaction product is passed through It is dry at 80 DEG C after ageing, washing, filtering, obtain nickel cobalt lithium aluminate persursor material；

(2) the lithium position doping vario-property of potassium ion: by resulting nickel cobalt lithium aluminate persursor material, lithium hydroxide and potassium sulfate After mixing under oxygen atmosphere 700 DEG C of 20 h of calcining, crushed 200 mesh screens, obtain the nickel cobalt lithium aluminate anode of doping vario-property Material；Wherein the molar ratio of nickel cobalt lithium aluminate persursor material and lithium hydroxide is 1:1.01, and potassium sulfate and lithium hydroxide rub You are than being 0.01:1；

(3) lithium-containing compound clad is constructed: 0.03 g(0.0015 mol) ammonium phosphate is dissolved in 60 mL dehydrated alcohols In, it is uniformly dispersed, the 10.0 g(0.11 mol of nickel cobalt aluminic acid lithium material after doping vario-property is added in Xiang Shangshu solution), at 70 DEG C Under conditions of be stirred to react 6 h, be dried to obtain powder at 100 DEG C, dry powder crushes after cooling in 200 DEG C of 10 h of calcining, obtains height The nickel cobalt lithium aluminate cathode material of multiplying power.

Under the conditions of 0.2 C, the specific discharge capacity of gained nickel cobalt lithium aluminate cathode material is 190 mAh/g, 100 circle of circulation Afterwards, specific discharge capacity is 182 mAh/g, has preferable cycle performance.

Embodiment 4

The preparation method of the high magnification nickel cobalt lithium aluminate cathode material of the present embodiment, steps are as follows:

(1) preparation of nickel cobalt lithium aluminate presoma: 85:15 weighs nickel nitrate and cobalt nitrate crystals in molar ratio, is dissolved in water After be uniformly mixed, concentration of metal ions is 2.0 mol/L, and the aluminum nitrate for weighing 5mol is dissolved in 4 mol/L ammonium hydroxide and 8 mol/L In the mixed solution of sodium hydroxide, two kinds of mixed solutions are injected in the reaction kettle containing bottom liquid simultaneously, control entire reactant For the pH value of system 10.0 ± 0.02, mixing speed is 700 r/min, reacts 8 h, and temperature is 50 DEG C, and reaction product is by old Change, wash, after filtering, it is dry at 120 DEG C, obtain nickel cobalt lithium aluminate persursor material；

(2) the lithium position doping vario-property of potassium ion: by resulting nickel cobalt lithium aluminate persursor material, lithium acetate, potassium acetate and After the mixing of carbonic acid potassium dihydrogen, 750 DEG C of 13 h of calcining, crushed 200 mesh screens, obtain the nickel of doping vario-property under oxygen atmosphere Cobalt lithium aluminate cathode material；Wherein the molar ratio of nickel cobalt lithium aluminate persursor material and lithium acetate is 1:1.04, potassium acetate and carbon Acid dihydride potassium (molar ratio 1:2) is as a whole 0.03:1 with the molar ratio of lithium acetate；

(3) lithium-containing compound clad is constructed: by 0.1 g ammonium phosphate (0.00049 mol), 0.08 g diammonium hydrogen phosphate (0.00061 mol) and 0.05 g ammonium metavanadate (0.00043 mol) are dissolved in 60 mL dehydrated alcohols, are uniformly dispersed, Xiang Shangshu The 10.0 g(0.11 mol of nickel cobalt aluminic acid lithium material after doping vario-property is added in solution), 10 are stirred to react under conditions of 50 DEG C H, powder is dried to obtain at 100 DEG C, and dry powder crushes after cooling in 400 DEG C of 5 h of calcining, obtaining powerful nickel cobalt lithium aluminate just Pole material.

Under the conditions of 0.2 C, the specific discharge capacity of gained nickel cobalt lithium aluminate cathode material is 185 mAh/g, 100 circle of circulation Afterwards, specific discharge capacity is 170 mAh/g, has preferable cycle performance.

Embodiment 5

The preparation method of the high magnification nickel cobalt lithium aluminate cathode material of the present embodiment, steps are as follows:

(1) preparation of nickel cobalt lithium aluminate presoma: 85:15 weighs nickel acetate and cobalt acetate crystal in molar ratio, is dissolved in water After be uniformly mixed, concentration of metal ions is 3.0 mol/L, and the aluminum acetate for weighing 5mol is dissolved in 6 mol/L ammonium hydroxide and 10 mol/ In the mixed solution of L sodium hydroxide, two kinds of mixed solutions are injected in the reaction kettle containing bottom liquid simultaneously, control entire reactant For the pH value of system 9.0 ± 0.02, mixing speed is 600 r/min, reacts 8 h, and temperature is 55 DEG C.The ageing of reaction product process, It is dry at 120 DEG C after washing, filtering, obtain nickel cobalt lithium aluminate persursor material；

(2) the lithium position doping vario-property of potassium ion: by resulting nickel cobalt lithium aluminate persursor material, lithium carbonate and bicarbonate two Potassium mixing after under oxygen atmosphere 750 DEG C of 15 h of calcining, crushed 200 mesh screens, obtaining the nickel cobalt lithium aluminate of doping vario-property just Pole material；Wherein the molar ratio of nickel cobalt lithium aluminate persursor material and lithium carbonate is 1:1, mole of bicarbonate dipotassium and lithium carbonate Than for 0.04:1；

(3) lithium-containing compound clad is constructed: that 0.12 g ammonium metavanadate (0.00034 mol) is dissolved in 60 mL is anhydrous In ethyl alcohol, it is uniformly dispersed, the 10.0 g(0.11 mol of nickel cobalt aluminic acid lithium material after doping vario-property is added in Xiang Shangshu solution), It is stirred to react 8 h under conditions of 60 DEG C, powder is dried to obtain at 100 DEG C, dry powder is crushed after cooling, obtained in 350 DEG C of 2 h of calcining To powerful nickel cobalt lithium aluminate cathode material.

Under the conditions of 0.2 C, the specific discharge capacity of gained nickel cobalt lithium aluminate cathode material is 178 mAh/g, 100 circle of circulation Afterwards, specific discharge capacity is 160 mAh/g, has preferable cycle performance.

Embodiment 6

The preparation method of the high magnification nickel cobalt lithium aluminate cathode material of the present embodiment, steps are as follows:

(1) preparation of nickel cobalt lithium aluminate presoma: 85:15 weighs nickel acetate and cobalt acetate crystal in molar ratio, is dissolved in water After be uniformly mixed, concentration of metal ions is 2.0 mol/L, and the aluminum acetate for weighing 5mol is dissolved in 5 mol/L ammonium hydroxide and 10 mol/ Two kinds of mixed solutions are injected in the reaction kettle containing bottom liquid simultaneously, control entire reaction system by the mixed solution of L sodium hydroxide PH value 10.0 ± 0.02, mixing speed is 500 r/min, reacts 8 h, and temperature is 50 DEG C, reaction product by ageing, It is dry at 120 DEG C after washing, filtering, obtain nickel cobalt lithium aluminate persursor material；

(2) the lithium position doping vario-property of potassium ion: by resulting nickel cobalt lithium aluminate persursor material, lithium hydroxide, carbonic acid two After hydrogen potassium, bicarbonate dipotassium and potassium carbonate mixing, 700 DEG C of 16 h of calcining, crushed 200 mesh screens, obtain under oxygen atmosphere The nickel cobalt lithium aluminate cathode material of doping vario-property；Wherein the molar ratio of nickel cobalt lithium aluminate persursor material and lithium hydroxide is 1: 1.05, carbonic acid potassium dihydrogen, bicarbonate dipotassium and potassium carbonate (molar ratio 0.8:1:1.2) as a whole with mole of lithium hydroxide Than for 0.04:1；

(3) lithium-containing compound clad is constructed: 0.6 g cobalt phosphate (0.0012 mol) is dissolved in 50 mL dehydrated alcohols In, it is uniformly dispersed, 10.0 g of nickel cobalt aluminic acid lithium material (0.11 mol) after doping vario-property is added in Xiang Shangshu solution, 85 It is stirred to react 5 h under conditions of DEG C, powder is dried to obtain at 100 DEG C, dry powder is crushed after cooling, obtained in 350 DEG C of 5 h of calcining Powerful nickel cobalt lithium aluminate cathode material.

Under the conditions of 0.2 C, the specific discharge capacity of gained nickel cobalt lithium aluminate cathode material is 160 mAh/g, 100 circle of circulation Afterwards, specific discharge capacity is 140 mAh/g.

Claims (6)

1. a kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material, it is characterised in that steps are as follows:
(1) preparation of nickel cobalt lithium aluminate persursor material: by uniformly mixed nickel, cobalt salt solution, and the ammonium hydroxide dissolved with aluminium salt It is injected in the reaction kettle containing bottom liquid simultaneously with sodium hydroxide mixed solution, the pH for controlling entire reaction system is 9-12, stirring Heating reaction 8-16 h, the solution after reaction passes through ageing, washing, filtering, dry at 80-120 DEG C, obtains nickel cobalt lithium aluminate Persursor material；
(2) the lithium position doping vario-property of potassium ion: by resulting nickel cobalt lithium aluminate persursor material and sylvite and lithium salts mixed calcining, It crushed 200 mesh screens, the nickel cobalt lithium aluminate cathode material after obtaining doping vario-property；
(3) lithium-containing compound clad is constructed: modifying agent being dissolved in dehydrated alcohol, is uniformly dispersed, doping is then added and changes Property after nickel cobalt lithium aluminate cathode material, be dried to obtain powder after being stirred to react 3-10 h under conditions of 50 ~ 100 DEG C, pass through Calcining, is cooled to room temperature, obtains high magnification nickel cobalt lithium aluminate cathode material；Nickel cobalt lithium aluminate presoma material in the step (2) Expect to be 1:1 ~ 1.05 with the molar ratio of lithium salts, the molar ratio of sylvite and lithium salts is 0.01 ~ 0.05:1.
2. the preparation method of high magnification nickel cobalt lithium aluminate cathode material according to claim 1, it is characterised in that: the step Suddenly the sylvite in (2) is one of potassium carbonate, carbonic acid potassium dihydrogen, bicarbonate dipotassium, potassium nitrate, potassium sulfate, potassium acetate or several Kind.
3. the preparation method of high magnification nickel cobalt lithium aluminate cathode material according to claim 1, it is characterised in that: the step Suddenly the calcination temperature in (2) is 700 DEG C ~ 850 DEG C, and calcination time is 10 ~ 20 h.
4. a kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material according to claim 1, it is characterised in that: institute Stating the modifying agent in step (3) is one of ammonium metavanadate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, cobalt phosphate or several Kind.
5. the preparation method of high magnification nickel cobalt lithium aluminate cathode material according to claim 1, it is characterised in that: the step Suddenly the molar ratio of the modifying agent in (3) and nickel cobalt lithium aluminate cathode material is 0.003 ~ 0.015:1.
6. the preparation method of high magnification nickel cobalt lithium aluminate cathode material according to claim 1, it is characterised in that: the step Suddenly the calcination temperature in (3) is 200 DEG C ~ 400 DEG C, and calcination time is 2 ~ 10h.
CN201710389952.0A 2017-05-26 2017-05-27 A kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material CN107093741B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201710384793 2017-05-26
CN2017103847935 2017-05-26

Publications (2)

Publication Number Publication Date
CN107093741A CN107093741A (en) 2017-08-25
CN107093741B true CN107093741B (en) 2019-06-21

Family

ID=59639776

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710389952.0A CN107093741B (en) 2017-05-26 2017-05-27 A kind of preparation method of high magnification nickel cobalt lithium aluminate cathode material

Country Status (1)

Country Link
CN (1) CN107093741B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107959004A (en) * 2017-10-23 2018-04-24 格林美（无锡）能源材料有限公司 A kind of anode material of lithium battery and preparation method of nitrogen-doped graphene and lithium molybdate
CN107910549A (en) * 2017-10-31 2018-04-13 中国科学院青海盐湖研究所 Positive electrode for lithium ion battery and its preparation method and application
CN108011100A (en) * 2017-12-15 2018-05-08 中国科学院成都有机化学有限公司 A kind of tertiary cathode material of surface reaction cladding and preparation method thereof
CN108314094B (en) * 2018-01-29 2020-02-07 蒋央芳 Preparation method of small-particle nickel cobalt aluminum hydroxide
CN109461907A (en) * 2018-10-09 2019-03-12 郑州中科新兴产业技术研究院 A kind of preparation method of nickelic tertiary cathode material
CN109449391A (en) * 2018-10-09 2019-03-08 郑州中科新兴产业技术研究院 A kind of high capacity class monocrystalline nickel cobalt lithium aluminate cathode material and preparation method thereof
CN109980203A (en) * 2019-03-29 2019-07-05 桂林理工大学 The method for improving nickelic tertiary cathode material chemical property by silica/sodium modified synergic
CN110048100A (en) * 2019-03-29 2019-07-23 桂林理工大学 The method for improving nickelic tertiary cathode material chemical property by magnesium fluoride/sodium modified synergic

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6770398B1 (en) * 2001-09-11 2004-08-03 The United States Of America As Represented By The Secretary Of The Army Potassium stabilized manganese dioxide for lithium rechargeable batteries
CN101264874A (en) * 2008-03-12 2008-09-17 周葛亮 Doping synthesis method for anode material ferric lithium phosphate
CN104091919A (en) * 2014-07-29 2014-10-08 中国科学院福建物质结构研究所 Positive electrode material for lithium ion battery and preparation method of positive electrode material
CN104900870A (en) * 2015-05-11 2015-09-09 田东 Preparation method of nickel cobalt lithium aluminate cathode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6770398B1 (en) * 2001-09-11 2004-08-03 The United States Of America As Represented By The Secretary Of The Army Potassium stabilized manganese dioxide for lithium rechargeable batteries
CN101264874A (en) * 2008-03-12 2008-09-17 周葛亮 Doping synthesis method for anode material ferric lithium phosphate
CN104091919A (en) * 2014-07-29 2014-10-08 中国科学院福建物质结构研究所 Positive electrode material for lithium ion battery and preparation method of positive electrode material
CN104900870A (en) * 2015-05-11 2015-09-09 田东 Preparation method of nickel cobalt lithium aluminate cathode material

Also Published As

Publication number Publication date
CN107093741A (en) 2017-08-25

Similar Documents

Publication Publication Date Title
CN104157831B (en) Lithium-rich manganese-based composite positive pole of the spinel nickel LiMn2O4 of a kind of core shell structure, stratiform and preparation method thereof
CN103280571B (en) A kind of anode material for lithium-ion batteries and preparation method thereof
CN104466154B (en) A kind of preparation method of lithium ion battery anode material nickel cobalt aluminium
CN103435105B (en) A kind of ferriferous oxide/carbon composition lithium ion battery cathode material and its preparation method and application
CN105958042B (en) A kind of fabricated in situ Li2MnO3The anode material for lithium-ion batteries and its synthetic method of coating modification
CN102044666B (en) Method for preparing lithium iron phosphate composite material for lithium cells
CN103490051B (en) One is applicable to high-tension multielement cathode lithium electric material and preparation method thereof
CN103928672B (en) A kind of positive electrode active material for lithium ion battery and preparation method thereof
CN100420088C (en) Lithium ion secondary cell with nickel-base anode active material and producing method thereof
CN102315429B (en) The preparation method of aluminum-doped material of cathode of lithium ion battery with solid phase process
CN102569780B (en) Method for preparing lithium ion battery cathode material with layered structure
CN104393285B (en) Nickel-cobalt-aluminum ternary positive electrode material and its preparation method
CN103474625B (en) A kind of Olivine-type Cathode Material in Li-ion Batteries method for coating of nucleocapsid structure
CN102810668B (en) Lithium ion battery nickel-cobalt-manganese ternary composite anode material and method for preparing precursor thereof
CN102583292B (en) Ferric phosphate having micro-nano structure and preparation method thereof as well as lithium iron phosphate material
CN105552344A (en) Positive plate of lithium ion battery, lithium ion battery and preparation method of lithium ion battery
CN103896339B (en) A kind of preparation method of sodium manganese oxide
CN102569781B (en) High-voltage lithium ion battery cathode material and preparation method thereof
CN102299328B (en) Metal fluoride cathode material of lithium secondary battery and preparation method of cathode material
WO2010091611A1 (en) Ni-, co- and mn- multi-doped positive material for lithium ion battery and preparation method thereof
CN104577093A (en) Surface coating modified lithium ion battery cathode material and preparation method thereof
CN102437311B (en) Lithium iron phosphate composite material, its preparation method and application
CN102386381A (en) Preparation method of nano positive material for lithium ion battery
CN103715424A (en) Core-shell structured cathode material and preparation method thereof
CN101941685B (en) Preparation of spherical lithium iron phosphate material and lithium ion battery using spherical lithium iron phosphate material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant