CN107221645A - Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof - Google Patents

Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof Download PDF

Info

Publication number
CN107221645A
CN107221645A CN201710544937.9A CN201710544937A CN107221645A CN 107221645 A CN107221645 A CN 107221645A CN 201710544937 A CN201710544937 A CN 201710544937A CN 107221645 A CN107221645 A CN 107221645A
Authority
CN
China
Prior art keywords
cathode material
ion battery
layered cathode
lithium ion
olivine
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
CN201710544937.9A
Other languages
Chinese (zh)
Inventor
杨成浩
欧星
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Towards Lithium Amperex Technology Ltd
Original Assignee
Guangzhou Towards Lithium Amperex Technology Ltd
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
Application filed by Guangzhou Towards Lithium Amperex Technology Ltd filed Critical Guangzhou Towards Lithium Amperex Technology Ltd
Priority to CN201710544937.9A priority Critical patent/CN107221645A/en
Publication of CN107221645A publication Critical patent/CN107221645A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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
    • 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

A kind of olivine-type structure LiNxPO4Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof.The chemical formula of the rich nickelic layered cathode material of the lithium ion battery is：LiNiaCobM1‑a‑bO2, LiNxPO4For finishing coat olivine-type material, preparation method is：First pass through liquid-phase coprecipitation and high-temperature solid-phase sintering method prepares the nickelic layered cathode material of pure phase lithium ion battery, the method being then combined using sol-gal process and low-temperature sintering method is by the LiN of olivine-type structurexPO4Equably coat and be doped to nickelic layered cathode material surface.The present invention is by using olivine-type structure LiNxPO4Layered cathode material nickelic to lithium ion battery carries out surface modification, can effectively improve its long-term cycle stability and high-temperature behavior, non-reversible deformation of the prepared material in cyclic process, and preparation method is simple to operate, environment-friendly, is adapted to industrial production.

Description

Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof
Technical field
The invention belongs to lithium ion battery electrode material preparing technical field, and in particular to olivine-type structure LiNxPO4Table Face modification nickelic layered cathode material of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is because its is environment-friendly, security performance is excellent, specific energy density is high, the features such as self discharge is small, Through being widely used in the fields such as portable type electronic product and electric automobile.In recent years, how lithium ion is further improved The energy density of battery, is to promote lithium ion battery in electric automobile and the wide variety of key of field of hybrid electric vehicles.Its In, the relatively low high-energy-density that directly results in of positive electrode specific capacity can not meet the requirement of long mileage electric automobile, be to hinder lithium The key factor that ion battery further develops.Therefore, study and improve the key that positive electrode is lithium ion battery development.
At present, commercialized tertiary cathode material because energy density is high and cycle performance is excellent, market gradually under Main flow positive electrode LiCoO drops2Shipment amount and improve ternary material output.Particularly, the nickelic positive electrode of stratiform (LiNiaCobM1-a-bO2) because its exceed 180mAh/g actual specific capacity and 3.7V high working voltages, excite wide spread interest and Pay close attention in market.But, it is not high enough to there is compacted density in the nickelic positive electrode of stratiform, it is impossible to play the advantage of energy density completely； Meanwhile, there is remaining alkali impurity in positive electrode surface, higher alkali content increases battery core preparation process difficulty, and causes High-temperature storage performance is not good.
Therefore it provides a kind of olivine-type structure LiNxPO4The nickelic layered cathode material of surface modification lithium ion battery and its Preparation method is not enough very necessary to solve prior art.
The content of the invention
Present invention aims at provide a kind of olivine-type structure LiNxPO4The nickelic stratiform of surface modification lithium ion battery is just Pole material and preparation method thereof, preparation method is simple to operate and friendly to environment, the olivine-type structure LiN obtainedxPO4Repair on surface The decorations nickelic layered cathode material of lithium ion battery can effectively improve the nickelic layered cathode material of lithium ion battery its cyclical stability, Be conducive to the deintercalation of lithium ion, suppress non-reversible deformation of the material in cyclic process.
The purpose of the present invention is realized by following technological means.
A kind of olivine-type structure LiN is providedxPO4The preparation side of the nickelic layered cathode material of surface modification lithium ion battery Method, comprises the following steps：
1) weigh nickel salt, cobalt salt and M metal salts to be dissolved separately in deionized water, it is 0.1-1mol/L to be configured to concentration Salting liquid；The nickel salt, cobalt salt and M metal salts are according to nickelic layered cathode material presoma chemical formula NiaCobM1-a-b (OH)2The mol ratio of middle Ni, Co and M element is weighed, wherein, a, b are molal quantity, 0.5≤a≤1,0≤b≤0.2 and 0.5≤a+ B≤1, M is the one or more in metal ion Al, Mn and V；
2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration For 1-5mol/L, the molar concentration of ammoniacal liquor is 0.5-2.5mol/L；
3) by step 2) obtained by mixed ammonium/alkali solutions be added in reactor, the volume of mixed ammonium/alkali solutions accounts for reactor volume 50%-80%, and control the pH value of liquid in reactor between 8-14, temperature is between 40-90 DEG C；
4) by step 1) nickel salt, cobalt salt and the M metal salt solutions that prepare at the uniform velocity add reactor respectively by peristaltic pump In, in whole process in reactor the pH value of liquid between 8-14, temperature is between 40-90 DEG C；
5) treat that nickel salt, cobalt salt and M metal salts are added completely into, it is still aging 12-24 hours after, then will precipitation filtering, wash Wash, dry；
6) by step 5) sediment after drying uniformly mixes with lithium salts, and the mol ratio of sediment and lithium salts is 1：1 to 1： 1.1；And in 450-600 DEG C of pre-burning 3-8 hours, then calcined 10-24 hours at 650-1000 DEG C, that is, obtain pure phase lithium-ion electric The nickelic layered cathode material LiNi in pondaCobM1-a-bO2；
7) by lithium source, N transition metal sources, phosphorus source, additive according to mol ratio 1：x：1：(0.1-2) is all dissolved in deionization In water, solution concentration is 0.1-5mol/L, then add step 6) obtained by the nickelic layered cathode material of pure phase lithium ion battery, Deionized water is evaporated at 80-120 DEG C, gel is formed；
8) by step 7) gained gel vacuum drying at 100-120 DEG C, crush, in 300 DEG C -500 DEG C of protective atmosphere Lower sintering 2-6 hours, that is, obtain olivine-type structure LiNxPO4The nickelic layered cathode material of surface modification lithium ion battery LiNiaCobM1-a-bO2。
It is preferred that, above-mentioned steps 1) in, the nickel salt is in nickel sulfate, nickel nitrate, nickel chloride, nickel oxalate and nickel acetate It is one or more；Cobalt salt is the one or more in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt oxalate and cobalt acetate；M metal salts are One or more in manganese salt, aluminium salt, vanadic salts.
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.
It is preferred that, above-mentioned steps 2) described in alkaline solution be sodium hydroxide solution, the mol ratio of sodium hydroxide and ammoniacal liquor For 2：1.
It is preferred that, above-mentioned steps 6) described in lithium salts be lithium hydroxide, lithium carbonate, lithium fluoride and lithium acetate in one kind or It is a variety of.
It is preferred that, above-mentioned steps 6) in be to be warming up to 450-600 DEG C with 2-10 DEG C/min heating rate, insulation 3-8 is small When, 650-1000 DEG C then is warming up to 3-8 DEG C/min heating rate again, 10-24 hours are incubated.
It is preferred that, above-mentioned steps 7) described in lithium source be lithium hydroxide, lithium dihydrogen phosphate, lithium acetate and lithium carbonate in one Plant or a variety of；
Step 7) described in N transition metal sources be vanadic salts, manganese salt, cobalt salt, nickel salt, aluminium salt, molybdenum salt, one kind of molysite or many Kind；
Step 7) described in phosphorus source be ammonium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium phosphate and phosphoric acid in one or more；Institute The additive stated is the one or more in glucose, citric acid, sucrose and tartaric acid.
It is preferred that, above-mentioned steps 8) in be to be warming up to 300-500 DEG C with 2-8 DEG C/min heating rate, insulation 2-6 is small When.
It is preferred that, above-mentioned steps 8) in protective gas be high pure nitrogen or high-purity argon gas one kind.
Another object of the present invention is to provide by olivine-type structure LiN made from above-mentioned preparation methodxPO4Surface modification The nickelic layered cathode material of lithium ion battery, the chemical formula of the rich nickelic layered cathode material of lithium ion battery is LiNiaCobM1-a- bO2, wherein a, b is molal quantity, and 0.5≤a≤1,0≤b≤0.2 and 0.5≤a+b≤1, M are one in metal ion Al, Mn and V Plant or several, LiNxPO4For finishing coat olivine-type material, wherein, x is molal quantity, 0.5≤x≤1.5, N be metal from One or more in sub- V, Mn, Co, Ni, Al, Mo and Fe, and control olivine-type structure LiNxPO4The quality of clad is The 0.5~15% of nickelic layered cathode material quality.
Compared with prior art, the invention has the advantages that and technique effect：
1st, the present invention is by using olivine-type structure LiNxPO4Layered cathode material nickelic to lithium ion battery carries out table Face is modified, and can effectively improve its cyclical stability, is conducive to the deintercalation of lithium ion, suppresses material irreversible in cyclic process Deformation；Reduce the direct contact of material and electrolyte and occur side reaction, so as to improve the battery security under its long-term circulation Energy, particularly high-temperature behavior.
2nd, preparation method abundant raw materials of the invention, with low cost, simple to operate, environment-friendly, it is adaptable to extensive Industrial 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.
It is LiV made from embodiment 2 in Fig. 12/3PO4The nickelic layered cathode material of surface modification lithium ion battery and contrast The XRD spectrum of the obtained nickelic layered cathode material of pure phase (before surface modification) of example.
Fig. 2 is olivine-type structure LiV made from the embodiment of the present invention 22/3PO4The high nickel dam of surface modification lithium ion battery The SEM figures of shape positive electrode.
It is LiV made from embodiment 2 in Fig. 32/3PO4The nickelic layered cathode material of surface modification lithium ion battery and contrast The obtained nickelic layered cathode material of pure phase (before surface modification) of example at normal temperatures with the discharge cycles under 0.1C current densities Curve map.
Fig. 4 is LiV made from embodiment 22/3PO4The nickelic layered cathode material of surface modification lithium ion battery and comparative example The obtained nickelic layered cathode material of pure phase (before surface modification) at normal temperatures with 1C current densities circulate 100 circle circulations Figure.
It is LiV made from embodiment 2 in Fig. 52/3PO4The nickelic layered cathode material of surface modification lithium ion battery and contrast The obtained nickelic layered cathode material of pure phase (before surface modification) of example at normal temperatures to circulate 80 circles under different current densities Circulation figure.
Fig. 6 is LiV made from embodiment 22/3PO4The nickelic layered cathode material of surface modification lithium ion battery and comparative example Circulation 100 circle in the case where 55 DEG C of high temperature is with 1C current densities of the obtained nickelic layered cathode material of pure phase (before surface modification) is followed Ring figure.
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 olivine-type structure LiNxPO4The preparation method of the nickelic layered cathode material of surface modification lithium ion battery, bag Include following steps：
1) weigh nickel salt, cobalt salt and M metal salts to be dissolved separately in deionized water, it is 0.1-1mol/L to be configured to concentration Salting liquid；The nickel salt, cobalt salt and M metal salts are according to nickelic layered cathode material presoma chemical formula NiaCobM1-a-b (OH)2The mol ratio of middle Ni, Co and M element is weighed, wherein, a, b are molal quantity, 0.5≤a≤1,0≤b≤0.2 and 0.5≤a+ B≤1, M is the one or more in metal ion Al, Mn and V；
2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration For 1-5mol/L, the molar concentration of ammoniacal liquor is 0.5-2.5mol/L；
3) by step 2) obtained by mixed ammonium/alkali solutions be added in reactor, the volume of mixed ammonium/alkali solutions accounts for reactor volume 50%-80%, and control the pH value of liquid in reactor between 8-14, temperature is between 40-90 DEG C；
4) by step 1) nickel salt, cobalt salt and the M metal salt solutions that prepare at the uniform velocity add reactor respectively by peristaltic pump In, in whole process in reactor the pH value of liquid between 8-14, temperature is between 40-90 DEG C；
5) treat that nickel salt, cobalt salt and M metal salts are added completely into, it is still aging 12-24 hours after, then will precipitation filtering, wash Wash, dry；
6) by step 5) sediment after drying uniformly mixes with lithium salts, and the mol ratio of sediment and lithium salts is 1：1 to 1： 1.1；And in 450-600 DEG C of pre-burning 3-8 hours, then calcined 10-24 hours at 650-1000 DEG C, that is, obtain pure phase lithium-ion electric The nickelic layered cathode material LiNi in pondaCobM1-a-bO2；
7) by lithium source, N transition metal sources, phosphorus source, additive according to mol ratio 1：x：1：(0.1-2) is all dissolved in deionization In water, solution concentration is 0.1-5mol/L, then add step 6) obtained by the nickelic layered cathode material of pure phase lithium ion battery, Deionized water is evaporated at 80-120 DEG C, gel is formed；
8) by step 7) gained gel vacuum drying at 100-120 DEG C, crush, in 300 DEG C -500 DEG C of protective atmosphere Lower sintering 2-6 hours, that is, obtain olivine-type structure LiNxPO4The nickelic layered cathode material of surface modification lithium ion battery LiNiaCobM1-a-bO2。
Specifically, step 1) in, nickel salt is one kind or many in nickel sulfate, nickel nitrate, nickel chloride, nickel oxalate and nickel acetate Kind；Cobalt salt is the one or more in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt oxalate and cobalt acetate；M metal salts are manganese salt, aluminium One or more in salt, vanadic salts.
Specifically, step 2) in, alkaline solution is one or both of sodium hydroxide solution and potassium hydroxide solution.When Alkaline solution is sodium hydroxide solution, and the mol ratio of sodium hydroxide and ammoniacal liquor is preferably 2：1.
Specifically, step 6) lithium salts be lithium hydroxide, lithium carbonate, lithium fluoride and lithium acetate in one or more.
Step 6) in be to be warming up to 450-600 DEG C with 2-10 DEG C/min heating rate, be incubated 3-8 hours, then again with 3-8 DEG C/min heating rate is warming up to 650-1000 DEG C, is incubated 10-24 hours.
Specifically, step 7) lithium source be lithium hydroxide, lithium dihydrogen phosphate, lithium acetate and lithium carbonate in one kind or many Kind；N transition metal sources are vanadic salts, manganese salt, cobalt salt, nickel salt, aluminium salt, molybdenum salt, the one or more of molysite；Phosphorus source is biphosphate One or more in ammonium, ammonium hydrogen phosphate, ammonium phosphate and phosphoric acid；Described additive is glucose, citric acid, sucrose and winestone One or more in acid.
Specifically, step 8) in be to be warming up to 300-500 DEG C with 2-8 DEG C/min heating rate, be incubated 2-6 hours.Step It is rapid 8) in protective gas be high pure nitrogen or high-purity argon gas one kind.
The present invention is by using olivine-type structure LiNxPO4Layered cathode material nickelic to lithium ion battery carries out surface Modification, can effectively improve its cyclical stability, be conducive to the deintercalation of lithium ion, suppress irreversible shape of the material in cyclic process Become.The present invention can reduce the direct contact of material and electrolyte and occur side reaction, so as to improve the electricity under its long-term circulation Pond security performance, particularly high-temperature behavior.In addition, the preparation method abundant raw materials of the present invention, with low cost, it is simple to operate, It is environment-friendly, it is adaptable to large-scale industrial production.
Embodiment 2.
A kind of olivine-type structure LiNxPO4The preparation method of the nickelic layered cathode material of surface modification lithium ion battery, bag Include following steps：
1. according to the nickelic layered cathode material presoma chemical formula Ni of stratiform0.6Co0.2Mn0.2(OH)2In ratio Ni：Co： Mn=0.6:0.2:0.2 mol ratio weighs 1.2mol nickel sulfates, 0.4mol cobaltous sulfates and 0.4mol manganese sulfates and is dissolved in respectively In deionized water, the salting liquid that concentration is 0.2mol/L is configured to respectively.
2. 4mol NaOH solutions and 2mol ammonia solvents are configured to mixed ammonium/alkali solutions, NaOH solution in deionized water Concentration is 1mol/L, and ammonia concn is 0.5mol/L.
3. the mixed ammonium/alkali solutions that step 2 is obtained are added in reactor, its volume accounts for reactor volume 60%, and controls The pH value of liquid is that 10, temperature is 60 DEG C in reactor processed.
Reacted 4. the nickel sulfate that step 1 is prepared, cobaltous sulfate and manganese sulfate solution are at the uniform velocity added respectively by peristaltic pump It is 60 DEG C in 10, temperature that the pH value of liquid in reactor is controlled in kettle, in whole process.
5. treating that nickel sulfate, cobaltous sulfate and manganese sulfate solution have been added, after still aging 16 is small, by precipitation filtering, washing, dry It is dry.
6. sediment is well mixed with 2.1mol lithium hydroxides, the mol ratio of sediment and lithium salts is 1：1.05,500 After DEG C pre-burning 5 hours, calcined 15 hours at 850 DEG C, you can obtain the nickelic layered cathode material of pure phase lithium ion battery LiNi0.6Co0.2Mn0.2O2。
7. by 0.06mol lithium hydroxides, 0.04mol ammonium metavanadates, 0.06mol ammonium di-hydrogen phosphates and 0.06mol citric acids All it is dissolved in deionized water, adds prepared nickelic layered cathode material, be slowly evaporated at 90 DEG C, form gel.
8. by gained gel at 110 DEG C vacuum drying, crush, high pure nitrogen protection under 400 DEG C calcine 3 hours, i.e., Obtain olivine-type structure LiV2/3PO4The nickelic layered cathode material LiNi of surface modification lithium ion battery0.6Co0.2Mn0.2O2。
In order to carry out performance test, there is provided following comparative example 1.
Comparative example 1
1. according to the nickelic layered cathode material presoma chemical formula Ni of stratiform0.6Co0.2Mn0.2(OH)2Shown in Ni：Co：Mn =0.6:0.2:0.2 mol ratio weighs 1.2mol nickel sulfates, 0.4mol cobaltous sulfates and 0.4mol manganese sulfates and is dissolved in respectively In ionized water, the salting liquid that concentration is 0.2mol/L is configured to respectively.
2. 4mol NaOH solutions and 2mol ammonia solvents are configured to mixed ammonium/alkali solutions, NaOH solution in deionized water Concentration is 1mol/L, and ammonia concn is 0.5mol/L.
3. above-mentioned mixed ammonium/alkali solutions are added in reactor, its volume accounts for reactor volume 60%, and control ph It it is 60 DEG C for 10, temperature.
4. the nickel sulfate, cobaltous sulfate and manganese sulfate solution of above-mentioned preparation are at the uniform velocity added into reactor respectively by peristaltic pump In, control ph is 60 DEG C in 10, temperature in whole process.
5. treating that nickel sulfate, cobaltous sulfate and manganese sulfate solution have been added, after still aging 16 is small, by precipitation filtering, washing, dry It is dry.
6. sediment is well mixed with 2.1mol lithium hydroxides, (mol ratio of sediment and lithium salts is 1：1.05), exist After 500 DEG C of pre-burnings 5 hours, calcined 15 hours at 850 DEG C, you can obtain the nickelic layered cathode material of pure phase lithium ion battery LiNi0.6Co0.2Mn0.2O2。
As can be seen that the nickelic layered cathode material LiNi of lithium ion battery from Fig. 1 XRD spectrum0.6Co0.2Mn0.2O2For Typical layer structure, crystallinity is high.LiV2/3PO4The nickelic layered cathode material of surface modification lithium ion battery LiNi0.6Co0.2Mn0.2O2For typical layer structure, crystallinity height also demonstrates LiV2/3PO4Cladding is without result in nickelic stratiform Cathode material structure changes.From Fig. 2 SEM it can be seen from the figure thats, the nickelic layered cathode material of lithium ion battery LiNi0.6Co0.2Mn0.2O2It is that high compact is spherical, particle diameter is 15-20 microns.LiV2/3PO4The high nickel dam of surface modification lithium ion battery Shape positive electrode LiNi0.6Co0.2Mn0.2O2It is that high compact is spherical, particle diameter is 15-19 microns.
Result from Fig. 3 to Fig. 6, it can be seen that：
At 25 DEG C of normal temperature, charge-discharge test, the nickelic layered cathode of lithium ion battery are carried out in the case where multiplying power is 0.1C multiplying powers Material LiNi0.6Co0.2Mn0.2O2Initial discharge specific capacity be 174.2mAh/g, and the LiV of the present embodiment2/3PO4Surface modification The nickelic layered cathode material LiNi of lithium ion battery0.6Co0.2Mn0.2O2Initial discharge specific capacity be 179.1mAh/g, better than pair The result of ratio.
Charge-discharge test is carried out in the case where multiplying power is 1C multiplying powers, after 100 times circulate, the nickelic layered cathode of lithium ion battery Material LiNi0.6Co0.2Mn0.2O2Specific discharge capacity is 145.4mAh/g, and circulation conservation rate is about 88.5%.And the present embodiment LiV2/3PO4The nickelic layered cathode material LiNi of surface modification lithium ion battery0.6Co0.2Mn0.2O2Specific discharge capacity is 160.2mAh/g, circulation conservation rate is about 89.2%.
With 1C, 2C, 5C, when the big multiplying power such as 10C carries out charge-discharge test, the nickelic layered cathode material of lithium ion battery LiNi0.6Co0.2Mn0.2O specific discharge capacities can reach 160.4mAh/g, 152.9mAh/g, 141.3mAh/g, 134.3mAh/ respectively g.Discharge capacity is 149.8mAh/g after circulation 100 is enclosed using under 1C multiplying powers at 55 DEG C.And the LiV of the present embodiment2/3PO4Surface Modify the nickelic layered cathode material LiNi of lithium ion battery0.6Co0.2Mn0.2O2With 1C, 2C, 5C, the big multiplying power such as 10C is filled During discharge test, its specific discharge capacity can reach 164.8mAh/g, 156.8mAh/g, 149.5mAh/g, 143.7mAh/g respectively. Discharge capacity is 161.5mAh/g after circulation 100 is enclosed using under 1C multiplying powers at 55 DEG C.
To sum up comparing result can be seen that the LiV of the present embodiment2/3PO4The nickelic layered cathode of surface modification lithium ion battery Material LiNi0.6Co0.2Mn0.2O2With excellent chemical property.Its stable cycle performance, the cell safety under long-term circulation Performance is high, and particularly high-temperature behavior is excellent.In addition, the preparation method abundant raw materials of the present invention, with low cost, it is simple to operate, It is environment-friendly, it is adaptable to large-scale industrial production.
Embodiment 3.
1. according to the nickelic layered cathode material presoma chemical formula Ni of stratiform0.7Co0.28V0.02(OH)2Shown in Ni：Co：V =0.7:0.28:It is molten that 0.02 mol ratio weighs 0.7mol nickel nitrates, 0.28mol cobalt nitrates and 0.02mol ammonium metavanadates respectively Solution in deionized water, is configured to the salting liquid that concentration is 0.15mol/L.
2. 2mol NaOH solutions and 1mol ammonia solvents are configured to mixed ammonium/alkali solutions, NaOH solution in deionized water Concentration is 3mol/L, and ammonia concn is 1.5mol/L.
3. above-mentioned mixed ammonium/alkali solutions are added in reactor, its volume accounts for reactor volume 50%, and control ph It it is 90 DEG C for 13, temperature.
4. the nickel nitrate, cobalt nitrate and ammonium metavanadate solution of above-mentioned preparation are at the uniform velocity added into reactor respectively by peristaltic pump In, control ph is 90 DEG C in 13, temperature in whole process.
5. treating that nickel nitrate, cobalt nitrate and ammonium metavanadate solution have been added, after still aging 24 is small, precipitation is filtered, washed, Drying.
6. sediment is well mixed with 0.53mol lithium carbonates, (mol ratio of sediment and lithium salts is 1：1.05), 500 After DEG C pre-burning 8 hours, calcined 24 hours at 800 DEG C, you can obtain the nickelic layered cathode material of pure phase lithium ion battery LiNi0.7Co0.28V0.02O2。
7. 0.02mol lithium carbonates, 0.02mol ferrous oxalates, 0.02mol phosphoric acid hydrogen ammonia and 0.04mol tartaric acid is whole It is dissolved in deionized water, adds prepared nickelic layered cathode material, be slowly evaporated at 120 DEG C, form gel.
8. by gained gel at 120 DEG C vacuum drying, crush, high-purity argon gas protection under 500 DEG C calcine 6 hours, i.e., Obtain olivine-type structure LiFePO4The nickelic layered cathode material LiNi of surface modification lithium ion battery0.7Co0.28V0.02O2。
As can be seen that LiFePO from XRD spectrum4The nickelic layered cathode material of surface modification lithium ion battery LiNi0.7Co0.28V0.02O2For typical layer structure, crystallinity height also indicates that LiFePO4Cladding is without result in nickelic stratiform Cathode material structure changes.From SEM it can be seen from the figure thats LiFePO4The nickelic layered cathode material of surface modification lithium ion battery Expect LiNi0.7Co0.28V0.02O2Be second particle be piled into it is spherical, particle diameter be 11-13 microns.
At 25 DEG C of normal temperature, charge-discharge test, LiFePO are carried out in the case where multiplying power is 0.1C multiplying powers4Surface modification lithium-ion electric The nickelic layered cathode material LiNi in pond0.7Co0.28V0.02O2Initial discharge specific capacity be 185mAh/g.In the case where multiplying power is 1C multiplying powers Charge-discharge test is carried out, after 100 times circulate, its specific discharge capacity is 164mAh/g, and circulation conservation rate is about 91.2%. With 1C, 2C, 5C, when the big multiplying power such as 10C carries out charge-discharge test, its specific discharge capacity can reach 179.8mAh/g respectively, 172.5mAh/g, 163.6mAh/g, 155.3mAh/g.At 55 DEG C using under 1C multiplying powers circulation 100 circle after discharge capacity as 156.6mAh/g, it is shown that excellent chemical property.
Embodiment 4.
1. according to the nickelic layered cathode material presoma chemical formula Ni of stratiform0.8Co0.1Mn0.1(OH)2Shown in Ni：Co：Mn =0.8:0.1:0.1 mol ratio weighs 0.8mol nickel chlorides, 0.1mol cobalt chlorides and 0.1mol manganese chlorides and is dissolved in respectively In ionized water, the salting liquid that concentration is 0.3mol/L is configured to.
2. 3mol NaOH solutions and 1.5mol ammonia solvents are configured into mixed ammonium/alkali solutions in deionized water, NaOH is molten Liquid concentration is 1.8mol/L, and ammonia concn is 0.9mol/L.
3. above-mentioned mixed ammonium/alkali solutions are added in reactor, its volume accounts for reactor volume 70%, and control ph It it is 50 DEG C for 9, temperature.
4. the nickel chloride, cobalt chloride and manganese chloride solution of above-mentioned preparation are at the uniform velocity added into reactor respectively by peristaltic pump In, control ph is 50 DEG C in 9, temperature in whole process.
5. nickel to be chlorinated, cobalt chloride and manganese chloride solution have been added, after still aging 12 is small, by precipitation filtering, washing, dry It is dry.
6. sediment is well mixed with 1.08mol lithium fluoride, (mol ratio of sediment and lithium salts is 1：1.05), 550 After DEG C pre-burning 5 hours, calcined 18 hours at 750 DEG C, you can obtain the nickelic layered cathode material of pure phase lithium ion battery LiNi0.8Co0.1Mn0.1O2。
7. 0.02mol lithium acetates, 0.02mol cobalt acetates, 0.02mol phosphoric acid ammonia and 0.02mol sucrose are all dissolved in In ionized water, prepared nickelic layered cathode material is added, is slowly evaporated at 90 DEG C, gel is formed.
8. by gained gel at 100 DEG C vacuum drying, crush, 450 DEG C calcine 3 hours, that is, obtain olivine-type knot Structure LiCoPO4The nickelic layered cathode material LiNi of surface modification lithium ion battery0.8Co0.1Mn0.1O2。
As can be seen that LiCoPO from XRD spectrum4The nickelic layered cathode material of surface modification lithium ion battery LiNi0.8Co0.1Mn0.1O2For typical layer structure, crystallinity height also indicates that LiCoPO4Cladding is without result in nickelic stratiform Cathode material structure changes.From SEM it can be seen from the figure thats LiCoPO4The nickelic layered cathode material of surface modification lithium ion battery Expect LiNi0.8Co0.1Mn0.1O2Be second particle be piled into it is spherical, particle diameter be 13-15 microns.
At 25 DEG C of normal temperature, charge-discharge test, LiCoPO are carried out in the case where multiplying power is 0.1C multiplying powers4Surface modification lithium-ion electric The nickelic layered cathode material LiNi in pond0.8Co0.1Mn0.1O2Initial discharge specific capacity be 202mAh/g.In the case where multiplying power is 1C multiplying powers Charge-discharge test is carried out, after 100 times circulate, its specific discharge capacity is 171.3mAh/g, and circulation conservation rate is about 93.7%. With 1C, 2C, 5C, when the big multiplying power such as 10C carries out charge-discharge test, its specific discharge capacity can reach 182.8mAh/g respectively, 176.5mAh/g, 163.3mAh/g, 157.4mAh/g.At 55 DEG C using under 1C multiplying powers circulation 100 circle after discharge capacity as 177.6mAh/g, it is shown that excellent chemical property.
Embodiment 5.
1. according to the nickelic layered cathode material presoma chemical formula Ni of stratiform0.85Co0.1Al0.05(OH)2Shown in Ni：Co： Al=0.85:0.1:0.05 mol ratio weighs 1.7mol nickel oxalates, 0.2mol cobalt oxalates and the dissolving of 0.05mol aluminum sulfate respectively In deionized water, it is configured to the salting liquid that concentration is 0.2mol/L.
2. 1mol NaOH solutions and 0.5mol ammonia solvents are configured into mixed ammonium/alkali solutions in deionized water, NaOH is molten Liquid concentration is 0.8mol/L, and ammonia concn is 0.4mol/L.
3. above-mentioned mixed ammonium/alkali solutions are added in reactor, its volume accounts for reactor volume 55%, and control ph It it is 55 DEG C for 9, temperature.
4. the nickel oxalate, cobalt oxalate and aluminum sulfate solution of above-mentioned preparation are at the uniform velocity added into reactor respectively by peristaltic pump In, control ph is 55 DEG C in 10, temperature in whole process.
5. treating that nickel oxalate, cobalt oxalate and aluminum sulfate solution have been added, after still aging 20 is small, by precipitation filtering, washing, dry It is dry.
6. sediment is well mixed with 2.1mol lithium hydroxides, (mol ratio of sediment and lithium salts is 1：1.05), exist After 550 DEG C of pre-burnings 6 hours, calcined 15 hours at 750 DEG C, you can obtain the nickelic layered cathode material of pure phase lithium ion battery LiNi0.85Co0.1Al0.05O2。
7. 0.01mol lithium dihydrogen phosphates, 0.01mol aluminium chloride, 0.01mol phosphoric acid and 0.015mol glucose is all molten In deionized water, prepared nickelic layered cathode material is added, is slowly evaporated at 90 DEG C, gel is formed.
8. by gained gel at 110 DEG C vacuum drying, crush, 400 DEG C calcine 3 hours, that is, obtain olivine-type knot Structure LiAlPO4The nickelic layered cathode material LiNi of surface modification lithium ion battery0.85Co0.1Al0.05O2。
As can be seen that LiAlPO from XRD spectrum4The nickelic layered cathode material of surface modification lithium ion battery LiNi0.85Co0.1Al0.05O2For typical layer structure, crystallinity height also indicates that LiAlPO4Cladding is without result in high nickel dam Shape cathode material structure changes.From SEM it can be seen from the figure thats LiAlPO4The nickelic layered cathode of surface modification lithium ion battery Material LiNi0.85Co0.1Al0.05O2Be second particle be piled into it is spherical, particle diameter be 11-14 microns.
At 25 DEG C of normal temperature, charge-discharge test, LiAlPO are carried out in the case where multiplying power is 0.1C multiplying powers4Surface modification lithium-ion electric The nickelic layered cathode material LiNi in pond0.85Co0.1Al0.05O2Initial discharge specific capacity be 205mAh/g.It is 1C multiplying powers in multiplying power Lower carry out charge-discharge test, after 100 times circulate, its specific discharge capacity is 176.2mAh/g, and circulation conservation rate is about 93.9%.With 1C, 2C, 5C, when the big multiplying power such as 10C carries out charge-discharge test, its specific discharge capacity can reach respectively 187.6mAh/g, 179.4mAh/g, 168.4mAh/g, 160.3mAh/g.With electric discharge after the circle of circulation 100 under 1C multiplying powers at 55 DEG C Capacity is 175.8mAh/g, it is shown that excellent chemical property.
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 olivine-type structure LiNxPO4The preparation method of the nickelic layered cathode material of surface modification lithium ion battery, it is special Levy and be, comprise the following steps：
1) nickel salt, cobalt salt and M metal salts are weighed to be dissolved separately in deionized water, the salt that concentration is 0.1-1mol/L is configured to Solution；The nickel salt, cobalt salt and M metal salts are according to nickelic layered cathode material presoma chemical formula NiaCobM1-a-b(OH)2In The mol ratio of Ni, Co and M element is weighed, wherein, a, b are molal quantity, 0.5≤a≤1,0≤b≤0.2 and 0.5≤a+b≤1, M For the one or more in metal ion Al, Mn and V；
2) alkaline solution and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Wherein, alkaline solution concentration is 1- 5mol/L, the molar concentration of ammoniacal liquor is 0.5-2.5mol/L；
3) by step 2) obtained by mixed ammonium/alkali solutions be added in reactor, the volume of mixed ammonium/alkali solutions accounts for reactor volume 50%-80%, and control the pH value of liquid in reactor between 8-14, temperature is between 40-90 DEG C；
4) by step 1) nickel salt, cobalt salt and the M metal salt solutions that prepare at the uniform velocity added in reactor respectively by peristaltic pump, whole During individual in reactor the pH value of liquid between 8-14, temperature is between 40-90 DEG C；
5) treat that nickel salt, cobalt salt and M metal salts are added completely into, it is still aging 12-24 hours after, then will precipitation filtering, washing, dry It is dry；
6) by step 5) sediment after drying uniformly mixes with lithium salts, and the mol ratio of sediment and lithium salts is 1：1 to 1：1.1； And in 450-600 DEG C of pre-burning 3-8 hours, then calcined 10-24 hour at 650-1000 DEG C, that is, obtain pure phase lithium ion battery height Nickel layered cathode material LiNiaCobM1-a-bO2；
7) by lithium source, N transition metal sources, phosphorus source, additive according to mol ratio 1：x：1：(0.1-2) is all dissolved in deionized water In, solution concentration is 0.1-5mol/L, then add step 6) obtained by the nickelic layered cathode material of pure phase lithium ion battery, Deionized water is evaporated at 80-120 DEG C, gel is formed；
8) by step 7) gained gel vacuum drying at 100-120 DEG C, crush, burnt under 300 DEG C -500 DEG C of protective atmosphere Knot 2-6 hours, that is, obtain olivine-type structure LiNxPO4The nickelic layered cathode material of surface modification lithium ion battery LiNiaCobM1-a-bO2。
2. olivine-type structure LiN according to claim 1xPO4The nickelic layered cathode material of surface modification lithium ion battery Preparation method, it is characterised in that：Step 1) in, the nickel salt is nickel sulfate, nickel nitrate, nickel chloride, nickel oxalate and nickel acetate In one or more；Cobalt salt is the one or more in cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt oxalate and cobalt acetate；M metals Salt is the one or more in manganese salt, aluminium salt, vanadic salts.
3. olivine-type structure LiN according to claim 1xPO4The nickelic layered cathode material of surface modification lithium ion battery Preparation method, it is characterised in that：Step 2) described in alkaline solution be sodium hydroxide solution and potassium hydroxide solution in one Plant or two kinds.
4. olivine-type structure LiN according to claim 1xPO4The nickelic layered cathode material of surface modification lithium ion battery Preparation method, it is characterised in that：Step 2) described in alkaline solution be sodium hydroxide solution, mole of sodium hydroxide and ammoniacal liquor Than for 2：1.
5. olivine-type structure LiN according to claim 1xPO4The nickelic layered cathode material of surface modification lithium ion battery Preparation method, it is characterised in that：Step 6) described in lithium salts be lithium hydroxide, lithium carbonate, lithium fluoride and lithium acetate in one Plant or a variety of.
6. olivine-type structure LiN according to claim 1xPO4The nickelic layered cathode material of surface modification lithium ion battery Preparation method, it is characterised in that：Step 6) in be to be warming up to 450-600 DEG C with 2-10 DEG C/min heating rate, be incubated 3-8 Hour, 650-1000 DEG C then is warming up to 3-8 DEG C/min heating rate again, 10-24 hours are incubated.
7. olivine-type structure LiN according to claim 1xPO4The nickelic layered cathode material of surface modification lithium ion battery Preparation method, it is characterised in that step 7) described in lithium source be lithium hydroxide, lithium dihydrogen phosphate, lithium acetate and lithium carbonate in One or more；
Step 7) described in N transition metal sources be vanadic salts, manganese salt, cobalt salt, nickel salt, aluminium salt, molybdenum salt, the one or more of molysite；
Step 7) described in phosphorus source be ammonium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium phosphate and phosphoric acid in one or more；Described Additive is the one or more in glucose, citric acid, sucrose and tartaric acid.
8. olivine-type structure LiN according to claim 1xPO4The nickelic layered cathode material of surface modification lithium ion battery Preparation method, it is characterised in that：Step 8) in be to be warming up to 300-500 DEG C with 2-8 DEG C/min heating rate, be incubated 2-6 Hour.
9. olivine-type structure LiN according to claim 1xPO4The nickelic layered cathode material of surface modification lithium ion battery Preparation method, it is characterised in that：Step 8) in protective gas be high pure nitrogen or high-purity argon gas one kind.
10. the olivine-type structure LiN as made from any one of claim 1-9 preparation methodxPO4Surface modification lithium-ion electric The nickelic layered cathode material in pond, it is characterised in that：The chemical formula of the rich nickelic layered cathode material of lithium ion battery is LiNiaCobM1-a-bO2, wherein a, b is molal quantity, 0.5≤a≤1,0≤b≤0.2 and 0.5≤a+b≤1, M be metal ion Al, One or more in Mn and V, LiNxPO4For finishing coat olivine-type material, wherein, x is molal quantity, 0.5≤x≤ 1.5, N be the one or more in metal ion V, Mn, Co, Ni, Al, Mo and Fe, and controls olivine-type structure LiNxPO4 The quality of clad is the 0.5~15% of nickelic layered cathode material quality.
CN201710544937.9A 2017-07-06 2017-07-06 Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof Pending CN107221645A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710544937.9A CN107221645A (en) 2017-07-06 2017-07-06 Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710544937.9A CN107221645A (en) 2017-07-06 2017-07-06 Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof

Publications (1)

Publication Number Publication Date
CN107221645A true CN107221645A (en) 2017-09-29

Family

ID=59951985

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710544937.9A Pending CN107221645A (en) 2017-07-06 2017-07-06 Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107221645A (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108695514A (en) * 2018-06-20 2018-10-23 湖南图强科技开发有限公司 A kind of anode material for lithium-ion batteries of good cycle and preparation method thereof
CN108711615A (en) * 2018-05-30 2018-10-26 广州朝锂新能源科技有限公司 Metal-doped ceria surface modifies the nickelic positive electrode of lithium ion battery
WO2019075910A1 (en) * 2017-10-20 2019-04-25 北京工业大学 Lithium-enriched layered oxide material having phase structure gradiently changing in proportion and preparation method therefor
CN110492096A (en) * 2019-08-26 2019-11-22 贵州大学 A kind of highly crystalline submicron order nickel-cobalt-manganternary ternary anode material and preparation method thereof
CN110518206A (en) * 2019-08-22 2019-11-29 湖北锂诺新能源科技有限公司 Manganese phosphate vanadium lithium and carbon coat the preparation method of nickel cobalt manganese aluminium composite positive pole altogether
CN110854384A (en) * 2019-11-26 2020-02-28 河北省科学院能源研究所 Preparation method of surface-modified nickel-based electrode material
CN111916693A (en) * 2020-06-28 2020-11-10 南昌大学 Method for preparing organic matter coated high-nickel cathode material
CN112054194A (en) * 2020-08-07 2020-12-08 西安理工大学 Phosphorus-modified lithium ion battery positive electrode material and preparation method and application thereof
CN112366317A (en) * 2020-10-27 2021-02-12 桑顿新能源科技有限公司 High-nickel composite material, preparation method thereof and lithium ion battery
WO2021037267A1 (en) * 2019-08-29 2021-03-04 孚能科技(赣州)股份有限公司 Core-shell structure lithium-ion battery positive electrode material, preparation method thereof, positive electrode plate, lithium-ion battery and application thereof
CN113488633A (en) * 2021-07-27 2021-10-08 广西师范大学 Titanium magnesium phosphate coated high-nickel ternary or lithium-rich manganese-based positive electrode material and preparation method thereof
CN114122344A (en) * 2020-08-28 2022-03-01 艾可普罗 Bm 有限公司 Positive electrode active material and lithium secondary battery including the same
JP2022063840A (en) * 2020-10-12 2022-04-22 エコプロ ビーエム カンパニー リミテッド Positive electrode active material and lithium secondary battery including the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102148373A (en) * 2011-03-02 2011-08-10 中国科学院化学研究所 Cathode material of lithium ion battery and preparation method thereof
CN105161705A (en) * 2015-06-29 2015-12-16 山东玉皇新能源科技有限公司 Lithium manganese phosphate-coated nickel-cobalt lithium manganate cathode material and preparation method thereof
CN105552324A (en) * 2015-12-15 2016-05-04 天津斯特兰能源科技有限公司 Preparation method for lithium iron phosphate coated lithium nickel cobalt manganese composite material
CN105591099A (en) * 2016-03-27 2016-05-18 华南理工大学 Lithium molybdate surface modified lithium ion battery nickel-rich positive pole material and preparation method thereof
CN105742622A (en) * 2016-03-27 2016-07-06 华南理工大学 Olivine-structured LiMPO<4> surface modification layered lithium-rich manganese-based positive electrode material and preparation method therefor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102148373A (en) * 2011-03-02 2011-08-10 中国科学院化学研究所 Cathode material of lithium ion battery and preparation method thereof
CN105161705A (en) * 2015-06-29 2015-12-16 山东玉皇新能源科技有限公司 Lithium manganese phosphate-coated nickel-cobalt lithium manganate cathode material and preparation method thereof
CN105552324A (en) * 2015-12-15 2016-05-04 天津斯特兰能源科技有限公司 Preparation method for lithium iron phosphate coated lithium nickel cobalt manganese composite material
CN105591099A (en) * 2016-03-27 2016-05-18 华南理工大学 Lithium molybdate surface modified lithium ion battery nickel-rich positive pole material and preparation method thereof
CN105742622A (en) * 2016-03-27 2016-07-06 华南理工大学 Olivine-structured LiMPO<4> surface modification layered lithium-rich manganese-based positive electrode material and preparation method therefor

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019075910A1 (en) * 2017-10-20 2019-04-25 北京工业大学 Lithium-enriched layered oxide material having phase structure gradiently changing in proportion and preparation method therefor
US11198621B2 (en) 2017-10-20 2021-12-14 Beijing University Of Technology Lithium-rich layered oxide material with phase structure gradient and its preparation method
CN108711615A (en) * 2018-05-30 2018-10-26 广州朝锂新能源科技有限公司 Metal-doped ceria surface modifies the nickelic positive electrode of lithium ion battery
CN108695514A (en) * 2018-06-20 2018-10-23 湖南图强科技开发有限公司 A kind of anode material for lithium-ion batteries of good cycle and preparation method thereof
CN110518206A (en) * 2019-08-22 2019-11-29 湖北锂诺新能源科技有限公司 Manganese phosphate vanadium lithium and carbon coat the preparation method of nickel cobalt manganese aluminium composite positive pole altogether
CN110518206B (en) * 2019-08-22 2022-10-28 湖北锂诺新能源科技有限公司 Preparation method of nickel-cobalt-manganese-aluminum composite positive electrode material coated with manganese-vanadium-lithium phosphate and carbon
CN110492096A (en) * 2019-08-26 2019-11-22 贵州大学 A kind of highly crystalline submicron order nickel-cobalt-manganternary ternary anode material and preparation method thereof
WO2021037267A1 (en) * 2019-08-29 2021-03-04 孚能科技(赣州)股份有限公司 Core-shell structure lithium-ion battery positive electrode material, preparation method thereof, positive electrode plate, lithium-ion battery and application thereof
CN110854384B (en) * 2019-11-26 2021-04-02 河北省科学院能源研究所 Preparation method of surface-modified nickel-based electrode material
CN110854384A (en) * 2019-11-26 2020-02-28 河北省科学院能源研究所 Preparation method of surface-modified nickel-based electrode material
CN111916693A (en) * 2020-06-28 2020-11-10 南昌大学 Method for preparing organic matter coated high-nickel cathode material
CN111916693B (en) * 2020-06-28 2022-05-20 南昌大学 Method for preparing organic matter coated high-nickel cathode material
CN112054194A (en) * 2020-08-07 2020-12-08 西安理工大学 Phosphorus-modified lithium ion battery positive electrode material and preparation method and application thereof
CN112054194B (en) * 2020-08-07 2021-12-17 西安理工大学 Phosphorus-modified lithium ion battery positive electrode material and preparation method and application thereof
CN114122344A (en) * 2020-08-28 2022-03-01 艾可普罗 Bm 有限公司 Positive electrode active material and lithium secondary battery including the same
JP2022063840A (en) * 2020-10-12 2022-04-22 エコプロ ビーエム カンパニー リミテッド Positive electrode active material and lithium secondary battery including the same
JP7366966B2 (en) 2020-10-12 2023-10-23 エコプロ ビーエム カンパニー リミテッド Positive electrode active material and lithium secondary battery containing the same
CN112366317A (en) * 2020-10-27 2021-02-12 桑顿新能源科技有限公司 High-nickel composite material, preparation method thereof and lithium ion battery
CN112366317B (en) * 2020-10-27 2022-08-30 湖南桑瑞新材料有限公司 High-nickel composite material, preparation method thereof and lithium ion battery
CN113488633A (en) * 2021-07-27 2021-10-08 广西师范大学 Titanium magnesium phosphate coated high-nickel ternary or lithium-rich manganese-based positive electrode material and preparation method thereof
CN113488633B (en) * 2021-07-27 2022-05-31 广西师范大学 Titanium magnesium phosphate coated high-nickel ternary or lithium-rich manganese-based positive electrode material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN107221645A (en) Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof
US10957903B2 (en) Layered lithium-rich manganese-based cathode material with olivine structured LIMPO4 surface modification and preparation method thereof
CN107275620A (en) One kind is mixed with modification lithium-ion battery stratiform nickel-rich positive pole material and preparation method thereof
CN103078109A (en) Gradient coated LiNiO2 material and preparation method
CN103000878B (en) Gradient doped type lithium-ion cathode material and method for preparing same
CN104710302B (en) Oxalic acid ferrimanganic presoma of grade doping and preparation method thereof
CN107293744A (en) A kind of high voltage class monocrystalline tertiary cathode material and preparation method thereof
CN102214819B (en) Method for manufacturing cobalt nickel lithium manganate oxide as gradient anode active material of lithium ion battery
CN102881874B (en) Method for preparing lithium-rich solid solution cathode material through reduction
CN107591529A (en) A kind of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof
CN103367724A (en) Lithium iron phosphate cell material with core-shell structure, and preparation method thereof
CN104835957B (en) Preparation method of high-nickel ternary material used for lithium ion battery
CN104037413A (en) Preparation method of positive electrode material (carbon-coated iron-manganese-lithium phosphate) of lithium ion battery
CN102034967A (en) Coprecipitation preparation method of nickel manganese lithium oxide of anode material of high-voltage lithium battery
CN114784236B (en) Coated Al and F co-doped monocrystalline lithium manganate positive electrode material and preparation method and application thereof
CN109546131A (en) NCMA core-NCM shell positive electrode, preparation method and purposes
CN107204426A (en) A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property
CN103107328A (en) Preparation method of modified spinel type lithium manganate
CN103943862A (en) Binary layered lithium ion battery cathode material coated with phosphate and preparing method thereof
CN112340785B (en) Doped high-nickel ternary material and preparation method thereof
CN103682275A (en) Preparation method for LiVOPO4-Li3V2(PO4 )3 composite cathode material of lithium ion battery
CN106684350B (en) Preparation method of high-voltage positive electrode material lithium nickel manganese oxide
CN102881889B (en) Method for preparing lithium-enriched solid solution cathode material by two-section direct temperature-rise sintering
CN109461930B (en) Gradient-structured multi-component material for lithium ion battery and preparation method thereof
CN102881878B (en) Method for preparing lithium-rich solid solution cathode material by virtue of metal reduction process

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20170929

RJ01 Rejection of invention patent application after publication