CN101436663A - Composite anode material for lithium ion battery and preparation method thereof - Google Patents

Composite anode material for lithium ion battery and preparation method thereof Download PDF

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CN101436663A
CN101436663A CNA200810072407XA CN200810072407A CN101436663A CN 101436663 A CN101436663 A CN 101436663A CN A200810072407X A CNA200810072407X A CN A200810072407XA CN 200810072407 A CN200810072407 A CN 200810072407A CN 101436663 A CN101436663 A CN 101436663A
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lithium ion
ion battery
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廖代伟
符显珠
彭红丰
王新
黄令
柯福生
林敬东
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Xiamen University
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Xiamen University
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Abstract

The invention relates to a composite positive pole material of a lithium ion cell and a method for preparing the same, in particular to a cell positive pole material. The invention provides the composite positive pole material of the lithium ion cell and a method for preparing the same, wherein the composite positive pole material uses high valence state CoOOH coated NiOOH as a precursor to synthesize a composite phase with a nucleocapsid under low temperature air atmosphere. LiNiO2 is used as a nucleus, and LiCoO2 is used as a shell. The method comprises the following steps: preparing a cobalt sulfate solution which is mixed with spherical beta phase nickel hydroxide to obtain a serous fluid A; preparing a sodium hydroxide or potassium hydroxide solution to obtain a solution B; preparing an ammonia solution as a solution C; reacting the A and the B with the C to generate a solid-liquid mixture, performing solid-liquid separation, precipitating, washing and drying the solid to obtain spherical Ni(OH)2 and Co(OH)2 of a nucleocapsid structure, reacting the spherical Ni(OH)2 and Co(OH)2 with potassium persulphate in the NaOH or KOH solution to generate a black solid-liquid mixture, performing the solid-liquid separation, and washing and drying the black solid to obtain spherical NiOOH and CoOOH; and then mixing the spherical NiOOH and CoOOH with LiOH, and performing tablet forming and calcination to obtain the product.

Description

Lithium ion battery composite cathode material and preparation method thereof
Technical field
The present invention relates to a kind of cell positive material, especially relate to a kind of lithium ion battery composite cathode material and preparation method thereof.
Background technology
Lithium ion battery is just developed rapidly because of its excellent performance in commercialization success back and is used.Positive electrode accounts for space of top prominence in the lithium ion battery cost, and directly influences the performances such as capacity, useful life and voltage platform of battery.Mainly be cobalt-lithium oxide (LiCoO in the anode material for lithium-ion batteries at present 2), but cobalt resource lacks, price is expensive, and environment is had pollution, so the research of the honest and clean anode material for lithium-ion batteries of property favorable rates is very much urgent and important.Nickel oxide lithium (LiNiO 2), manganese oxide lithium (LiMn 2O 4), LiFePO4 (LiFePO 4) wait series material to obtain very big concern, wherein nickel oxide lithium series material has advantages such as capacity height, power are big, moderate cost, is very potential replacement LiCoO 2The anode material for lithium-ion batteries system.Yet LiNiO 2Synthetic difficult, shortcomings such as capacity attenuation is fast, poor heat stability are also arranged, thereby influence its practicability.
LiNiO 2The series material prior synthesizing method is after the salt with lithium salts and divalent nickel salt and other doped chemical mixes, to carry out high-temperature calcination under 700～900 ℃.The method easily generates the non-metering product that compares, reduce the layer structure of material, cause material property to worsen, this be because: there is bigger potential barrier in the trivalent Ni that the divalence Ni in (1) nickel salt commonly used will be oxidized to product, even under oxidizing atmosphere, also be difficult to, and adopt oxygen atmosphere to be unfavorable for the large-scale industrial production of material by complete oxidation; (2) at high temperature, LiNiO 2Be easy to undergo phase transition and decomposition loses electro-chemical activity.
Simple LiNiO 2Itself also exist some to be unfavorable for that it becomes the factor of commercialization battery material: (1) is because divalence Ni is more stable than trivalent Ni, at LiNiO 2In be easy to the existence of divalence Ni, it is to cause non-metering reason than product that divalence Ni exists, and can cause LiNiO 2Material has bigger irreversible capacity when initial charge/discharge and cycle performance worsens.(2) LiNiO 2In charge and discharge process repeatedly phase transformation can take place, material is shunk and expand, reduce the electrode cyclical stability, cause capacity attenuation.(3) at charging later stage LiNiO 2In trivalent Ni can be oxidized to tetravalence Ni, tetravalence Ni oxidizability is very strong, can oxidation Decomposition electrolyte, the corrosion collector is emitted heat and gas, causes safety issue.(4) LiNiO 2Itself is alkaline high, is easy in depositing process and airborne H 2O and CO 2Reaction (this reaction can cause the quality of material to increase, and the weightening finish situation when we store under the constant temperature and humidity condition with material is come its storage stability of comparison) causes material property to worsen.
The existing many reports of relevant lithium ion battery composite cathode material.Publication number provides a kind of lithium ion battery composite cathode material LiFePO for the application for a patent for invention of CN101252185 4The preparation method, with lithium carbonate, 2 oxalic acid hydrates are ferrous, ammonium dihydrogen phosphate, stoichiometric proportion batching by certain as dopant ion, adds the first body epoxy resin or the phenolic resins of carbon with rare earth element yttrium, with the absolute ethyl alcohol is the medium ball milling, in inert atmosphere, behind 300～400 ℃ of predecomposition 4～6h, be cooled to room temperature, after mixing once more, 600～700 ℃ of synthetic reaction 16～20h in inert atmosphere obtain having the cancellated yttrium composite positive pole LiFePO that contains 4/ C.LiFePO 4 according to this preparation method preparation has bigger electron conduction ability and specific area, and first discharge specific capacity can reach 160mAh/g under the room temperature.
Publication number provides a kind of lithium ion battery composite cathode material and preparation method thereof for the application for a patent for invention of CN1564347, and its molecular formula is as follows: LiM xFe 1～xPO 4/ (C+M '), wherein, M is Co, Mn, Cr, Ni, Cu, Ag or Au, M ' is Co, Mn, Cr, Ni, Cu, Ag or Au, 0＜X≤0.2.This invention is mixed with colloidal sol with needed raw material, then with reducing agent with the metal ions M in the colloidal sol ' N+Be reduced into metal simple-substance, formed gel after the colloidal sol drying is calcined in inert gas atmosphere, make the organic substance in the gel be cracked into conductive carbon black; Like this, ferric phosphate (II) lithium, metal simple-substance have formed LiM jointly with carbon black xFe 1～xPO 4/ (C+M ') composite material, thus guaranteed that metal simple-substance and carbon black are at composite positive pole LiM xFe 1～xPO 4Be uniformly dispersed among/(C+M ').
Publication number contains lithium-containing transition metal oxide, carbon nanotube and binding agent for the application for a patent for invention of CN1688051 provides a kind of anode material for lithium-ion batteries and preparation method thereof.Described method is according to 80%～90% with lithium-containing transition metal oxide, carbon nanotube, carbon black and binding agent, 3%～10%, 0%～8%, 3%～10% mass ratio mixes, dissolving downward modulation form slurry at organic solvent, again slurry is coated on the aluminium foil, through getting electrode diaphragm after roll-in, the vacuumize.The prepared combination electrode material of the present invention has the characteristics of high power capacity, high cyclical stability and high charge-discharge magnification.In voltage range is 3.0～4.5V, charge-discharge magnification 1C discharges and recharges under the condition, this composite positive pole discharge capacity first reaches 180～230mAh/g, cycle efficieny is greater than 85% first, capacitance loss rate after 20 circulations is less than 8%, under the charge-discharge magnification of 2C, discharge capacity reaches 170～200mAh/g first, and cycle efficieny is greater than 85% first.
Publication number provides a kind of lithium ion battery composite cathode material LiFePO for the application for a patent for invention of CN101114709 4～Li 3V 2(PO 4) 3/ C and preparation method thereof, complex chemical compound LiFePO 4～Li 3V 2(PO 4) 3LiFePO among the/C 4And Li 3V 2(PO 4) 3Be stoichiometric compound, and LiFePO 4And Li 3V 2(PO 4) 3Amount of substance is than being LiFePO 4/ Li 3V 2(PO 4) 3=1/x, 0＜x≤1.With LiOHH 2O, Li 2CO 3Perhaps CH 3COOLi2H 2O and FePO 44H 2O, V 2O 5, NH 4H 2PO 4Mix with polyethylene glycol, add furnishing rheology phase behind the water then, the roasting temperature 3～20h in 600～800 ℃ in inert atmosphere obtains anode material for lithium-ion batteries LiFePO with gained rheology phase predecessor 4～Li 3V 2(PO 4) 3/ C, the lithium ion battery composite cathode material capacity of preparation is big, efficiency for charge-discharge is high, cycle efficieny good, high rate capability is good, is fit to suitability for industrialized production.
Summary of the invention
The objective of the invention is problem at nickel oxide lithium tradition solid phase high-temperature calcination synthetic method needs high temperature, oxygen atmosphere, the defective etc. that easily generates non-metering compound, layer structure difference and simple nickel oxide lithium existence itself is unfavorable for its commercialization practicality, providing a kind of is presoma with high valence state CoOOH coating NiOOH, synthesizes in Cryogenic air atmosphere to have lithium ion battery composite cathode material of the compound phase of nucleocapsid and preparation method thereof.
Technical scheme of the present invention is to be coated on cobalt hydroxide and the nickel hydroxide composite particulate material that forms nucleocapsid structure on the ball-shape nickel hydroxide particle with cobalt hydroxide, is designated as Ni (OH) 2@Co (OH) 2, then this particle being carried out oxidation, the hydroxy cobalt oxide that obtains trivalent coats the nucleocapsid structure spheric granules of hydroxy nickel oxide, is designated as NiOOH@CoOOH.Spherical compound phase NiOOH@CoOOH of nucleocapsid and LiOH have synthesized rich Co under Cryogenic air atmosphere be shell, and rich Ni is designated as LiNiO for the nickel oxide lithium～cobalt-lithium oxide nucleocapsid structure composite positive pole of nuclear 2@LiCoO 2
Lithium ion battery composite cathode material LiNiO of the present invention 2@LiCoO 2With LiNiO 2Be nuclear, LiCoO 2Be shell, press mass ratio, LiNiO 2With LiCoO 2Proportioning be 100: (50～10).
Lithium ion battery composite cathode material LiNiO of the present invention 2@LiCoO 2The preparation method may further comprise the steps:
1) compound concentration is the cobaltous sulfate (CoSO of/1～5M 4) solution, and with spherical beta phase nickel hydroxide (Ni (OH) 2) mix, obtain slurries A;
2) NaOH (NaOH) or potassium hydroxide (KOH) solution of preparation 1～5M get solution B;
3) ammonia spirit of preparation 10%～20% is a solution C;
4) slurries A, solution B and solution C are added in the reactor, get solidliquid mixture after the reaction;
5) solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, and the solid precipitation is washed with water, dries, and promptly obtains the spherical Ni (OH) of nucleocapsid structure 2@Co (OH) 2
6) with the spherical Ni (OH) that obtains 2@Co (OH) 2In NaOH or KOH solution with potassium peroxydisulfate (K 2S 2O 8) react, get the black solidliquid mixture;
7) the black solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, and with the black solid washing, drying promptly obtains spherical Ni OOH@CoOOH;
8) spherical Ni OOH@CoOOH and LiOH are mixed, compacting is calcined in flakes, promptly obtains nucleocapsid structure composite positive pole LiNiO 2@LiCoO 2
In molar ratio, the proportioning of cobalt and nickel is preferably (10～50): 100.
In step 4), the pH of the reactant liquor in the reactor is preferably 10.5～12, and the temperature of reaction is preferably 30～80 ℃, and the time of reaction is preferably 2～24h.
In step 5), the temperature of oven dry is preferably 50～120 ℃.
In step 6), the concentration of NaOH or KOH solution is preferably 1～5M, presses mass ratio, K 2S 2O 8Best in quality be Ni (OH) 2@Co (OH) 22～5 times, the temperature of reaction is preferably 20～80 ℃, the time of reaction is preferably 1～24h.
In step 7), dry temperature is preferably 50～100 ℃.
In step 8), press mass ratio, the consumption of LiOH is preferably 1.05 times of spherical Ni OOH@CoOOH, and the temperature of calcining is preferably 500～650 ℃, and the time of calcining is preferably 24～48h.
Spherical nucleocapsid LiNiO of the present invention 2@LiCoO 2Composite positive pole and synthetic method thereof have following advantage:
1) adopts LCoO 2Be shell and LiNiO 2Be the complex method of nuclear, LCoO 2The very strong high price nickel of oxidizability that had generated when shell both can have been avoided charging directly contacts with electrolyte, thereby the reaction of infringement battery takes place, and can isolate LiNiO again 2When storing, directly contact, thereby can improve the storage stability of material with external environment such as air.
2) without divalent nickel salt but the divalent nickel salt pre-oxidation is become trivalent, so not only directly avoided the existence of nickelous in the product, reduce the non-metering ratio of product, improve the layer structure of product; And can not be used in and carry out high temperature under the oxygen and prepare the nickel oxide lithium anode material, both avoided the climax reaction to cause product to take place to send out mutually, calcination reaction is simplified.
Description of drawings
Fig. 1 is by spherical Ni OOH@CoOOH, NiOOH and Ni (OH) 2The XRD figure for preparing the product that obtains at 600 ℃ of following LiOH reaction 24h etc. different presomas.In Fig. 1, abscissa is Scattering angle (2 θ °) CuK α, and ordinate is intensity I ntensity; Curve a.NiOOH@CoOOH; B.NiOOH; C.Ni (OH) 2As can be seen from Figure 1, NiOOH@CoOOH is the p-ratio maximum of (003)/(104) of the product of presoma, is 1.79, and layer structure is best, and the raw material complete reaction prepares the LNiO of good layer structure 2With LCoO 2Composite material; The product that spherical β～NiOOH is a presoma takes second place, and is 1.24, has good layer structure; And spherical Ni (OH) 2For the product minimum of presoma, be 0.69, layer structure is very poor.
Fig. 2 is spherical nucleocapsid LiNiO of the present invention 2@LiCoO 2The SEM photo of composite positive pole.In Fig. 2, scale is 10 μ m, and reaction temperature is 600 ℃.
Fig. 3 is spherical nucleocapsid LiNiO of the present invention 2@LiCoO 2The EDS elementary analysis figure of composite positive pole.In Fig. 3, abscissa is Distance (μ m), and ordinate is Intensity (A.u.); Reaction temperature is 600 ℃, and upper curve is Ni, and lower curve is Co.
As can be seen, it is spherical in shape to prepare resulting material from Fig. 2 and 3, and the Co constituent content from edge to the center of ball step-down and the Ni constituent content is just in time opposite gradually, this just illustrates that composite material has LNiO 2Be nuclear LCoO 2Structure for shell.
Embodiment
Embodiment 1
Compound concentration is the CoSO of 1M 4Solution, and with spherical β Ni (OH) mutually 2Mix, obtain slurries A.Wherein the mol ratio of cobalt and nickel is 10: 100; The NaOH solution of preparation 1M gets solution B; The ammonia spirit of preparation 10% is a solution C; Solution A, B and C are added respectively in the reactor, and the pH of control reactant liquor is 10.5, and the temperature of reactant liquor is 60 ℃, and the reaction time is 4h; The solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, solid precipitate with deionized water washes clean, promptly obtains the spherical Ni (OH) of nucleocapsid structure 120 ℃ of following oven dry 2@Co (OH) 2With the spherical Ni (OH) that obtains 2@Co (OH) 2In the KOH of 1M solution with K 2S 2O 8Reaction, K 2S 2O 8Quality is Ni (OH) 2@Co (OH) 22 times, reaction temperature is 60 ℃, the reaction time is 4h, the black solidliquid mixture; The black solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, the black solid washes clean, is drying to obtain spherical Ni OOH@CoOOH at 80 ℃; The LiOH of spherical Ni OOH@CoOOH and 1.05 times is mixed, and compacting is calcined in stove and is promptly obtained nucleocapsid structure composite positive pole LiNiO in flakes 2@LiCoO 2, calcining heat is 600 ℃, the time is 24h.Resulting sample is designated as NC01, and its performance is referring to table 1.
Table 1
The sample name First discharge specific capacity Discharge and recharge capability retention 20 times Weightening finish % ratio when sample is stored in 30 ℃ of 55% humidity
NC01 181.8mAhg ～1 92.1％ 2.8％
NC02 186.2mAhg ～1 91.8％ 2.5％
NC03 189.5mAhg ～1 93.5％ 2.2％
NC04 183.7mAhg ～1 94.1％ 2.1％
NC05 178.1mAhg ～1 95.6％ 2.1％
DB01 81.5mAhg ～1 6.2％
DB02 182.6mAhg ～1 89％ 4.6％
Embodiment 2
Compound concentration is the CoSO of 3M 4Solution, and with spherical β Ni (OH) mutually 2Mix, obtain slurries A.Wherein the mol ratio of cobalt and nickel is 20: 100; The KOH solution of preparation 5M gets solution B; The ammonia spirit of preparation 20% is a solution C; Solution A, B and C are added respectively in the reactor, and the pH of control reactant liquor is 11, and the temperature of reactant liquor is 30 ℃, and the reaction time is 24h; The solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, solid precipitate with deionized water washes clean, promptly obtains the spherical Ni (OH) of nucleocapsid structure 50 ℃ of following oven dry 2@Co (OH) 2With the spherical Ni (OH) that obtains 2@Co (OH) 2In the NaOH of 2M solution with K 2S 2O 8Reaction, K 2S 2O 8Quality is Ni (OH) 2@Co (OH) 23 times, reaction temperature is 30 ℃, the reaction time is 24h, the black solidliquid mixture; The black solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, the black solid washes clean, is drying to obtain spherical Ni OOH@CoOOH at 80 ℃; The LiOH of spherical Ni OOH@CoOOH and 1.05 times is mixed, and compacting is calcined in stove and is promptly obtained nucleocapsid structure composite positive pole LiNiO in flakes 2@LiCoO 2, calcining heat is 600 ℃, the time is 24h.Resulting sample is designated as NC02, and its performance is referring to table 1.
Embodiment 3
Compound concentration is the CoSO of 5M 4Solution, and with spherical β Ni (OH) mutually 2Mix, obtain slurries A.Wherein the mol ratio of cobalt and nickel is 30: 100; The KOH solution of preparation 3M gets solution B; The ammonia spirit of preparation 15% is a solution C; Solution A, B and C are added respectively in the reactor, and the pH of control reactant liquor is 12, and the temperature of reactant liquor is 80 ℃, and the reaction time is 2h; The solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, solid precipitate with deionized water washes clean, promptly obtains the spherical Ni (OH) of nucleocapsid structure 100 ℃ of following oven dry 2@Co (OH) 2With the spherical Ni (OH) that obtains 2@Co (OH) 2In the KOH of 5M solution with K 2S 2O 8Reaction, K 2S 2O 8Quality is Ni (OH) 2@Co (OH) 23 times, reaction temperature is 50 ℃, the reaction time is 12h, the black solidliquid mixture; The black solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, the black solid washes clean, is drying to obtain spherical Ni OOH@CoOOH at 80 ℃; The LiOH of spherical Ni OOH@CoOOH and 1.05 times is mixed, and compacting is calcined in stove and is promptly obtained nucleocapsid structure composite positive pole LiNiO in flakes 2@LiCoO 2, calcining heat is 650 ℃, the time is 24h.Resulting sample is designated as NC03, and its performance is referring to table 1.
Embodiment 4
Compound concentration is 2M CoSO 4Solution, and with spherical β Ni (OH) mutually 2Mix, obtain slurries A.Wherein the mol ratio of cobalt and nickel is 40: 100; The NaOH solution of preparation 2M gets solution B; The ammonia spirit of preparation 20% is a solution C; Solution A, B and C are added respectively in the reactor, and the pH of control reactant liquor is 12.5, and the temperature of reactant liquor is 40 ℃, and the reaction time is 12h; The solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, solid precipitate with deionized water washes clean, promptly obtains the spherical Ni (OH) of nucleocapsid structure 60 ℃ of following oven dry 2@Co (OH) 2With the spherical Ni (OH) that obtains 2@Co (OH) 2In the NaOH of 3M solution with K 2S 2O 8Reaction, K 2S 2O 8Quality is Ni (OH) 2@Co (OH) 25 times, reaction temperature is 30 ℃, the reaction time is 8h, the black solidliquid mixture; The black solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, the black solid washes clean, is drying to obtain spherical Ni OOH@CoOOH at 100 ℃; The LiOH of spherical Ni OOH@CoOOH and 1.05 times is mixed, and compacting is calcined in stove and is promptly obtained nucleocapsid structure composite positive pole LiNiO in flakes 2@LiCoO 2, calcining heat is 550 ℃, the time is 40h.Resulting sample is designated as NC04, and its performance is referring to table 1.
Embodiment 5
Compound concentration is 5M CoSO 4Solution, and with spherical β Ni (OH) mutually 2Mix, obtain slurries A.Wherein the mol ratio of cobalt and nickel is 50: 100; The KOH solution of preparation 5M gets solution B; The ammonia spirit of preparation 20% is a solution C; Solution A, B and C are added respectively in the reactor, and the pH of control reactant liquor is 12.5, and the temperature of reactant liquor is 20 ℃, and the reaction time is 24h; The solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, solid precipitate with deionized water washes clean, promptly obtains the spherical Ni (OH) of nucleocapsid structure 120 ℃ of following oven dry 2@Co (OH) 2With the spherical Ni (OH) that obtains 2@Co (OH) 2In the KOH of 5M solution with K 2S 2O 8Reaction, K 2S 2O 8Quality is Ni (OH) 2@Co (OH) 25 times, reaction temperature is 20 ℃, the reaction time is 24h, the black solidliquid mixture; The black solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, the black solid washes clean, is drying to obtain spherical Ni OOH@CoOOH at 50 ℃; The LiOH of spherical Ni OOH@CoOOH and 1.05 times is mixed, and compacting is calcined in stove and is promptly obtained nucleocapsid structure composite positive pole LiNiO in flakes 2@LiCoO 2, calcining heat is 500 ℃, the time is 48h.Resulting sample is designated as NC05, and its performance is referring to table 1.
Comparative Examples 1
With the spherical Ni (OH) that obtains 2Mix with 1.05 times LiOH, compacting is calcined in stove in flakes, and calcining heat is 600 ℃, and the time is 24h.Resulting sample is designated as DB01, and its performance is referring to table 1.
Comparative Examples 2
With spherical β phase Ni (OH) 2In the KOH of 1M solution with K 2S 2O 8Reaction, K 2S 2O 8Quality is Ni (OH) 2@Co (OH) 23 times, reaction temperature is 60 ℃, the reaction time is 4h, the black solidliquid mixture; The black solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, the black solid washes clean, is drying to obtain spherical Ni OOH at 100 ℃; The LiOH of spherical Ni OOH and 1.05 times is mixed, and compacting is calcined in stove in flakes, and calcining heat is 600 ℃, and the time is 24h.Resulting sample is designated as DB02, and its performance is referring to table 1.
As can be seen from Table 1, has LNiO 2Be nuclear, LCoO 2For the compound lithium ion positive electrode of shell not only has good specific discharge capacity, and have good charge-discharge performance and storge quality.Adopt niccolic NiOOH as presoma than divalence nickel (OH) 2It is better to obtain layer structure as the preparation raw material, the lithium ion battery lithium nickel oxygen positive electrode that chemical property is better.

Claims (10)

1. lithium ion battery composite cathode material is characterized in that with LiNiO 2Be nuclear, LiCoO 2Be shell, press mass ratio, LiNiO 2With LiCoO 2Proportioning be 100: 50～10.
2. the preparation method of lithium ion battery composite cathode material as claimed in claim 1 is characterized in that may further comprise the steps:
1) compound concentration is the cobalt sulfate solution of/1～5M, and mixes with spherical beta phase nickel hydroxide, obtains slurries A;
2) NaOH or the potassium hydroxide solution of preparation 1～5M get solution B;
3) ammonia spirit of preparation 10%～20% is a solution C;
4) slurries A, solution B and solution C are added in the reactor, get solidliquid mixture after the reaction;
5) solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, and the solid precipitation is washed with water, dries, and promptly obtains the spherical Ni (OH) of nucleocapsid structure 2@Co (OH) 2
6) with the spherical Ni (OH) that obtains 2@Co (OH) 2In NaOH or KOH solution, react, get the black solidliquid mixture with potassium peroxydisulfate;
7) the black solidliquid mixture that reaction is obtained carries out Separation of Solid and Liquid, and with the black solid washing, drying promptly obtains spherical Ni OOH@CoOOH;
8) spherical Ni OOH@CoOOH and LiOH are mixed, compacting is calcined in flakes, promptly obtains nucleocapsid structure composite positive pole LiNiO 2@LiCoO 2
3. the preparation method of lithium ion battery composite cathode material as claimed in claim 2 is characterized in that in molar ratio, and the proportioning of cobalt and nickel is 10～50: 100.
4. the preparation method of lithium ion battery composite cathode material as claimed in claim 2 is characterized in that in step 4), and the pH of the reactant liquor in the reactor is 10.5～12.
5. the preparation method of lithium ion battery composite cathode material as claimed in claim 2 is characterized in that in step 4), and the temperature of reaction is 30～80 ℃, and the time of reaction is 2～24h.
6. the preparation method of lithium ion battery composite cathode material as claimed in claim 2 is characterized in that in step 5), and the temperature of oven dry is 50～120 ℃.
7. the preparation method of lithium ion battery composite cathode material as claimed in claim 2 is characterized in that in step 6), and the concentration of NaOH or KOH solution is 1～5M.
8. the preparation method of lithium ion battery composite cathode material as claimed in claim 2 is characterized in that pressing mass ratio in step 6), K 2S 2O 8Quality be Ni (OH) 2@Co (OH) 22～5 times, the temperature of reaction is 20～80 ℃, the time of reaction is 1～24h.
9. the preparation method of lithium ion battery composite cathode material as claimed in claim 2 is characterized in that in step 7), and dry temperature is 50～100 ℃.
10. the preparation method of lithium ion battery composite cathode material as claimed in claim 2, it is characterized in that pressing mass ratio in step 8), the consumption of LiOH is 1.05 times of spherical Ni OOH@CoOOH, the temperature of calcining is 500～650 ℃, and the time of calcining is 24～48h.
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CN102040251A (en) * 2010-11-30 2011-05-04 辽宁九夷三普电池有限公司 Method for preparing cobalt clad beta-NiOOH by liquid phase oxidation method
CN102433033A (en) * 2011-09-02 2012-05-02 景德镇陶瓷学院 Method for preparing carbon black inclusion pigment in situ by nonhydrolytic sol-gel process
CN103296274A (en) * 2013-05-15 2013-09-11 中信国安盟固利电源技术有限公司 Coated nickel lithium cobalt oxide positive material with high capacity, low residual alkali and low pH value, and preparation method thereof
CN103311536A (en) * 2013-07-02 2013-09-18 先进储能材料国家工程研究中心有限责任公司 Preparation method of beta-type cobalt-coated nickel oxide hydroxide
CN103348510A (en) * 2010-11-12 2013-10-09 丰田自动车株式会社 Secondary battery
CN104577106A (en) * 2015-01-13 2015-04-29 辽宁大学 Positive pole material of lithium ion battery and preparation method of positive pole material
WO2015149211A1 (en) * 2014-03-31 2015-10-08 Showa Denko K.K. A positive electrode active material and a li secondary battery
CN107565123A (en) * 2017-08-22 2018-01-09 山东精工电子科技有限公司 A kind of nickel, cobalt, LiMn2O4 core-shell material gel and preparation method thereof
CN112614990A (en) * 2020-12-11 2021-04-06 格林美股份有限公司 Nickel-manganese binary composite positive electrode material and preparation method thereof
WO2023011672A1 (en) * 2021-08-06 2023-02-09 巴斯夫杉杉电池材料有限公司 Surface-coating precursor for lithium ion battery positive electrode material and preparation method therefor
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CN101916848A (en) * 2010-08-06 2010-12-15 山东久力电子科技有限公司 LiFePO4 coating LiMn2O4 composite electrode material and preparation method thereof
CN103348510B (en) * 2010-11-12 2016-01-13 丰田自动车株式会社 Secondary cell
CN103348510A (en) * 2010-11-12 2013-10-09 丰田自动车株式会社 Secondary battery
CN102040251A (en) * 2010-11-30 2011-05-04 辽宁九夷三普电池有限公司 Method for preparing cobalt clad beta-NiOOH by liquid phase oxidation method
CN102040251B (en) * 2010-11-30 2011-11-30 辽宁九夷三普电池有限公司 Method for preparing cobalt clad beta-NiOOH by liquid phase oxidation method
CN102433033B (en) * 2011-09-02 2014-03-05 景德镇陶瓷学院 Method for preparing carbon black inclusion pigment in situ by nonhydrolytic sol-gel process
CN102433033A (en) * 2011-09-02 2012-05-02 景德镇陶瓷学院 Method for preparing carbon black inclusion pigment in situ by nonhydrolytic sol-gel process
CN103296274B (en) * 2013-05-15 2016-06-15 中信国安盟固利电源技术有限公司 A kind of high power capacity, low residual alkali, low ph value cladded type lithium nickel cobalt dioxide positive electrode and preparation method thereof
CN103296274A (en) * 2013-05-15 2013-09-11 中信国安盟固利电源技术有限公司 Coated nickel lithium cobalt oxide positive material with high capacity, low residual alkali and low pH value, and preparation method thereof
CN103311536A (en) * 2013-07-02 2013-09-18 先进储能材料国家工程研究中心有限责任公司 Preparation method of beta-type cobalt-coated nickel oxide hydroxide
CN103311536B (en) * 2013-07-02 2016-03-23 先进储能材料国家工程研究中心有限责任公司 β type covers the preparation method of cobalt hydroxy nickel oxide
WO2015149211A1 (en) * 2014-03-31 2015-10-08 Showa Denko K.K. A positive electrode active material and a li secondary battery
CN104577106A (en) * 2015-01-13 2015-04-29 辽宁大学 Positive pole material of lithium ion battery and preparation method of positive pole material
CN107565123A (en) * 2017-08-22 2018-01-09 山东精工电子科技有限公司 A kind of nickel, cobalt, LiMn2O4 core-shell material gel and preparation method thereof
CN107565123B (en) * 2017-08-22 2023-10-17 山东精工电子科技股份有限公司 Nickel, cobalt and lithium manganate core-shell material gel and preparation method thereof
CN112614990A (en) * 2020-12-11 2021-04-06 格林美股份有限公司 Nickel-manganese binary composite positive electrode material and preparation method thereof
WO2023011672A1 (en) * 2021-08-06 2023-02-09 巴斯夫杉杉电池材料有限公司 Surface-coating precursor for lithium ion battery positive electrode material and preparation method therefor
WO2023036102A1 (en) * 2021-09-09 2023-03-16 深圳市贝特瑞纳米科技有限公司 Positive electrode material and preparation method therefor, positive electrode plate, and battery

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