CN106025254B - A kind of surface coating modification method of nickel lithium manganate cathode material - Google Patents

A kind of surface coating modification method of nickel lithium manganate cathode material Download PDF

Info

Publication number
CN106025254B
CN106025254B CN201610472512.7A CN201610472512A CN106025254B CN 106025254 B CN106025254 B CN 106025254B CN 201610472512 A CN201610472512 A CN 201610472512A CN 106025254 B CN106025254 B CN 106025254B
Authority
CN
China
Prior art keywords
lithium
ion doped
nickel
nickel ion
lithium salts
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.)
Active
Application number
CN201610472512.7A
Other languages
Chinese (zh)
Other versions
CN106025254A (en
Inventor
杨刚
王佳伟
李为立
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.)
Changshu Institute of Technology
Original Assignee
Changshu Institute of Technology
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 Changshu Institute of Technology filed Critical Changshu Institute of Technology
Priority to CN201610472512.7A priority Critical patent/CN106025254B/en
Publication of CN106025254A publication Critical patent/CN106025254A/en
Application granted granted Critical
Publication of CN106025254B publication Critical patent/CN106025254B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of methods of the surface coating modification of nickel lithium manganate cathode material, it includes the following steps: that lithium salts-coated by titanium dioxide nickel ion doped is first prepared, ammonium dihydrogen phosphate is added, is reacted to obtain lithium salts-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped;It is finally heated to 650~750 DEG C under air atmosphere, then cools to 400~600 DEG C and carries out second of heat treatment, after being cooled to room temperature, obtain positive electrode product.Fast-ionic conductor titanium phosphate lithium is coated on electrode material surface by the present invention, form artificial solid-state electrolyte layer, the effective erosion for inhibiting electrolyte to electrode material, improve the cyclical stability of material, furthermore fast-ionic conductor itself has good lithium ion conductive, improves cycle performance of electrode material under the conditions of high rate charge-discharge.

Description

A kind of surface coating modification method of nickel lithium manganate cathode material
Technical field
The invention belongs to technical field of chemistry and chemical engineering, and in particular to technical field of lithium ion, in particular to a kind of nickel The surface coating modification method of manganate cathode material for lithium.
Background technique
With the development that electric car is in recent years at full speed, lithium ion battery just receives more and more attention and develops.Nickel manganese Sour lithium (LiNi0.5Mn1.5O4) because it is with high voltage, high-energy density it is considered as next-generation lithium ion battery electrode material Important component.Nickel ion doped material generally has there are two types of crystal structure: it is a kind of belong to it is unordered LiNi0.5Mn1.5O4Fd3m space group forms octahedra 16d grid by the transition metal ions of random distribution, another belongs to Orderly LiNi0.5Mn1.5O4P4332 space group, nickel and manganese ion occupy 4a and 12d grid respectively.Ordered phase can hinder lithium from Son diffusion, and a small amount of Mn3+The unordered LiNi of ion0.5Mn1.5O4Electronic conductivity can be improved.However, Mn3+Electrolysis can be dissolved into To generate capacity attenuation in cyclic process in liquid, and the Ni of high-valence state2+/Ni4+Also electrolyte can be dissolved in, and electrolyte The HF of generation also can corroding electrode surface form thicker SEI film, especially under high magnification and hot conditions.Liu, J etc. [Liu,J.and A.Manthiram,Improved electrochemical performance of the 5V spinel cathode LiMn1.5Ni0.42Zn0.08O4by surface modification[J].Journal of The Electrochemical Society, 2009.156 (1): A66-A72] use Al2O3As face finish material, covering amount is 2%, it is prepared for Al2O3Coat nickel lithium manganate cathode material.Its cycle performance is effectively raised, after circulation 50 is enclosed, capacity is kept Rate reaches 99.5%, but modified electrode material lithium ion conductive is bad, and aluminium oxide sheet, cannot be effective as insulator Improve the big high rate performance of material.[Fan Y, Wang J, Tang Z, the et al.Effects of the such as Fan Y nanostructured SiO2 coating on the performance of LiNi0.5Mn1.5O4cathode materials for high-voltage Li-ion batteries[J].Electrochimica Acta,2007,52 (11): 3870-3875. SiO] is used2Nickel ion doped material is coated, when covering amount is 1%, after 100 circle of circulation, capacity retention ratio Reach 86%, effectively inhibits corrosion of the HF to electrode material, however SiO2A large amount of hydroxy functional group can promote again its with The problem of electrolyte reacts, and leads to electrolyte decomposition flatulence generation is faced with many difficulties in practical application.
To provide its ionic conductivity, therefore anode material for lithium-ion batteries needs to be added when being assembled into battery core electrolyte Positive electrode will form thicker solid-state electrolyte layer after being corroded by electrolyte, generate capacity attenuation in cyclic process.It is artificial solid State electrolyte layer is the effective ways for inhibiting electrolyte to corrode electrode material.There is nonmetallic oxidation commonly used in the substance of cladding Object, ZnO, Al2O3, BiOF, Bi2O3, SiO2And ZrO2;Phosphoric acid salt, such as Li3PO4, Li4P2O7, AlPO4, FePO4, and LiFePO4Deng.However most of metal oxide and phosphoric acid salt do not have ionic conductivity, therefore, the material after cladding Some shortcomings are understood on high rate performance, limitation is larger.
Summary of the invention
The purpose of the present invention is the purpose of the invention is to improve nickel lithium manganate cathode material in the electrolytic solution vulnerable to The problem of erosion, cycle performance reduce;By two step wet chemistry methods by titanium phosphate lithium (LiTi2(PO4)3) covering material attachment It in electrode material surface, is then heat-treated, forms the preparation method of fast-ionic conductor type solid-state electrolyte layer.
In order to solve the above technical problems, the surface coating modification side of a kind of nickel lithium manganate cathode material provided by the invention Method comprising following steps:
(1) mixture: lithium salts 0.1%~5%, alkyl titanate 3%~7%, nickel is matched according to following mass percent LiMn2O4 90%~95%;First lithium salts and alkyl titanate are dissolved in ethanol solution, nickel ion doped is then added, is stirred Lower heating is reacted under certain temperature, then solvent flashing, until being evaporated, obtains lithium salts-coated by titanium dioxide nickel mangaic acid Lithium;
(2) according to mass ratio 0.1~7:93~99.9, by lithium salts-titanium dioxide of ammonium dihydrogen phosphate and step (1) preparation The nickel ion doped mixing of cladding is scattered in deionized water, and mass percent is 10%~20%, stirring heating, under certain temperature It is reacted, then dries solution again, obtain lithium salts-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped;
(3) lithium salts-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped that step (2) obtains is put into aluminium oxide In crucible, it is heated to 650~750 DEG C of progress first time heat treatments under air atmosphere, keeps the temperature 3~8 hours, then cools to 400 ~600 DEG C carry out second and are heat-treated, and keep the temperature 3~8 hours, after being cooled to room temperature, obtain positive electrode product.
Preferably, the lithium salts is selected from one of lithium acetate, lithium carbonate and lithium hydroxide.
Preferably, the alkyl titanate is butyl titanate, further preferably tetrabutyl titanate.
Preferably, first time heat treatment temperature is 650~700 DEG C in step (3).
Preferably, second of heat treatment temperature is 400~500 DEG C in step (3).
Preferably, it is 2~10 DEG C/min that heating rate when being heat-treated for the first time is carried out in step (3).
Preferably, the nickel ion doped in the step (1) the preparation method comprises the following steps: weigh nickel acetate and manganese acetate respectively, add After entering deionized water dissolving, LiOH solution is instilled, adjusting pH value is 11-12, and co-precipitation solution is heated at 80 DEG C and is concentrated into It is thick, after dry, grinding, be placed in Muffle furnace 500 DEG C pre-burning 6 hours, then first heated up in 650 DEG C of -900 DEG C of ranges Cool down the reaction of heat preservation after heat preservation, and finally cooling obtains nickel acid manganese lithium.
In the preparation process of nickel ion doped are as follows: the weight part ratio of nickel acetate and manganese acetate is 1:2.5-3.5.And in Muffle furnace Product after 500 DEG C of pre-burnings, which is placed in high temperature reaction stove, keeps the temperature 3h at 700 DEG C, is warming up to 900 DEG C and insulation reaction 6h, is cooled to 650 DEG C and insulation reaction 6h.
Certainly the present invention used in nickel ion doped can also use it may occur to persons skilled in the art that existing skill Art is prepared.
Preferably, heat treatment for the first time and second of heat treatment time are 4~6h in step (3).
In currently preferred technical solution, in the step (1), reacted 2~5 hours at 60~80 DEG C.
In currently preferred technical solution, in the step (2), reacted 2~5 hours at 70~90 DEG C.
In currently preferred technical solution, in step (1), mixture: lithium salts is matched according to following mass percent 0.5%~2%, alkyl titanate 3%~5%, nickel ion doped 93%~95%.
The second aspect of the present invention provides a kind of nickel lithium manganate cathode material, is prepared by following steps:
(1) mixture: lithium salts 0.1%~5%, alkyl titanate 3%~7%, nickel is matched according to following mass percent LiMn2O4 90%~95%;First lithium salts and alkyl titanate are dissolved in ethanol solution, nickel ion doped is then added, is stirred Lower heating is reacted under certain temperature, then solvent flashing, until being evaporated, obtains lithium salts-coated by titanium dioxide nickel mangaic acid Lithium;
(2) according to mass ratio 0.1~7:93~99.9, by lithium salts-titanium dioxide of ammonium dihydrogen phosphate and step (1) preparation The nickel ion doped mixing of cladding is scattered in deionized water, and mass percent is 10%~20%, stirring heating, under certain temperature It is reacted, then dries solution again, obtain lithium salts-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped;
(3) lithium salts-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped that step (2) obtains is put into aluminium oxide In crucible, it is heated to 650~750 DEG C of progress first time heat treatments under air atmosphere, keeps the temperature 3~8 hours, then cools to 400 ~600 DEG C carry out second and are heat-treated, and keep the temperature 3~8 hours, after being cooled to room temperature, obtain positive electrode product.
In one embodiment of the invention, the lithium salts is lithium acetate.
It is a further object of the present invention to provide a kind of electrochemical cells, comprising:
(1) anode,
(2) electrolyte;
(3) cathode;Wherein cathode is made of the anode material for lithium-ion batteries of preceding method preparation;
(4) diaphragm.
The beneficial effects of the present invention are: nickel ion doped is as high-voltage anode material, wherein there are a small amount of Mn3+Ion Facilitate the ion conducting of electrode material, but is susceptible to the erosion of electrolyte and is dissolved in electrolyte.The present invention is by fast ion Conductor titanium phosphate lithium is coated on electrode material surface, forms artificial solid-state electrolyte layer, effective to inhibit electrolyte to electrode material The erosion of material improves the cyclical stability of material, and furthermore fast-ionic conductor itself has good lithium ion conductive, improves Cycle performance of electrode material under the conditions of high rate charge-discharge.
Detailed description of the invention
Fig. 1 is the scanning electron microscopy on nickel lithium manganate cathode material surface after titanium phosphate lithium cladding prepared by embodiment 2 Figure.Figure 1A is the scanning electron microscope (SEM) photograph for amplifying 7000 times, and Figure 1B is the scanning electron microscope (SEM) photograph for amplifying 1000 times.
Fig. 2 is the perseverance of nickel lithium manganate cathode material and uncoated sample after titanium phosphate lithium cladding prepared by embodiment 2 Current test results.
Fig. 3 is the nickel ion doped that in embodiment 1 prepared by step 1, embodiment 1 and embodiment 2 prepare through titanium phosphate lithium packet Cover the zoom rate test result of rear nickel ion doped sample.
Specific embodiment
The following examples are of the invention to be further described, but the contents of the present invention are without being limited thereto.Present invention explanation Embodiment in book is only used for that the present invention will be described, does not play restriction effect to protection scope of the present invention.This The protection scope of invention is only defined by the claims, and those skilled in the art are in embodiment disclosed by the invention on the basis of institute Any omission, replacement or the modification made fall within protection scope of the present invention.
Embodiment 1
(1) present invention implement coat needed for nickel ion doped preparation process are as follows: weigh respectively 1.25 parts by weight acetic acid nickel and 3.68 parts by weight acetic acid manganese are added in 80mL deionized water after being completely dissolved, and the LiOH that concentration is 1mol/L is instilled in 1 hour Solution 11mL, filling into appropriate ammonium hydroxide and adjusting pH value is 11-12, co-precipitation solution heat at 80 DEG C be concentrated into it is thick, turn Enter at 100 DEG C of air dry oven it is 6 hours dry, dried object by grinding be placed on Muffle furnace 500 DEG C, air atmosphere pre-burning 6 it is small When, pre-burning product is fully ground, in 5MPa pressure lower sheeting, sample strip is placed in high temperature reaction stove at 700 DEG C and keeps the temperature 3h, 900 DEG C and insulation reaction 6h are warming up to, is cooled to 650 DEG C and insulation reaction 6h, furnace cooling.Gained sample is fully ground standby With sample XRD test is shown to be nickel ion doped.
(2) 0.0043 parts by weight acetic acid lithium and 0.035 parts by weight tetrabutyl titanate are dissolved in ethanol solution, then 2 parts by weight of step 1 gained nickel ion doped are added, stirs lower heating, is reacted 2 hours at 60 DEG C, then solvent flashing, until steaming It is dry, obtain lithium acetate-coated by titanium dioxide nickel ion doped.
(3) according to mass ratio 1:99, by lithium acetate-dioxy prepared by 0.0178 parts by weight of phosphoric acid ammonium dihydrogen and step 1 The nickel ion doped mixing for changing titanium cladding is scattered in deionized water, and percent concentration range is 10%.Stirring heating, at 70 DEG C Reaction 2 hours, then dries solution again, obtains lithium acetate-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped.
(4) lithium acetate-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped that step 3 obtains is put into aluminium oxide In crucible, 650 DEG C are heated under air atmosphere, heating rate is 2 DEG C/min, keeps the temperature 3 hours, then cools to 400 DEG C, heat preservation 3 hours, after being cooled to room temperature, obtain positive product.Packed battery after being sliced is taken out, is tested.
Embodiment 2
(1) 0.0129g lithium acetate and 0.105g tetrabutyl titanate are dissolved in ethanol solution, nickel mangaic acid is then added Lithium 2g stirs lower heating, reacts 2 hours at 80 DEG C, then solvent flashing obtains lithium acetate-coated by titanium dioxide until being evaporated Nickel ion doped.
(2) according to mass ratio 3:97, by lithium acetate-titanium dioxide prepared by 0.0534g ammonium dihydrogen phosphate and step 1 The nickel ion doped mixing of cladding is scattered in deionized water, and percent concentration range is 20%.Stirring heating, reacts at 80 DEG C 5 hours, solution is then dried again, obtains lithium acetate-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped.
(3) lithium acetate-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped that step 2 obtains is put into aluminium oxide In crucible, 750 DEG C are heated under air atmosphere, heating rate is 5 DEG C/min, keeps the temperature 5 hours, then cools to 500 DEG C, heat preservation 5 hours, after being cooled to room temperature, obtain positive product.Packed battery after being sliced is taken out, is tested.
Attached drawing 1 is that the scanning electron on nickel lithium manganate cathode material surface after titanium phosphate lithium cladding prepared by embodiment 2 is aobvious Micro- figure.From the figure, it can be seen that material shows very well there is no significant change in cladding front and back particle macroscopic view and microstructure Spherical shape, between 10 to 20 microns, big ball exists simultaneously particle size with bead, such pattern when being fabricated to battery, Its tap density is opposite can be relatively high, and the capacity of single battery is larger.Each particle has hundreds of second particle again It accumulates, the surface microscopic topographic of particle is observed after amplification, it is seen that it is tightly combined between second particle, and has some gaps, It makes it possible to sufficiently and electrolyte contacts, and coating process not makes these gaps disappear, without too big change matrix Surface topography so that the material after cladding can also come into full contact with electrolyte, when charge and discharge, the transmission area of lithium ion will not It is much affected.
Attached drawing 2 is nickel lithium manganate cathode material and uncoated nickel mangaic acid after titanium phosphate lithium cladding prepared by embodiment 2 The constant current test result of lithium sample.In comparison, the sample of cladding is lower in a few circle capacity most started, may need derived from it Want more activation processs.But the sample after LiTi2 (PO4) 3 is coated then shows preferable cycle performance.By 100 circles After circulation, compared to the tenth circle, the capacity retention ratio of LNM is 85.5%, and the capacity retention ratio after LiTi2 (PO4) 3 is coated reaches 94.5%.
Embodiment 3
(1) 0.065g lithium acetate and 0.175g tetrabutyl titanate are dissolved in ethanol solution, nickel mangaic acid is then added Lithium 2g stirs lower heating, reacts 3 hours at 70 DEG C, then solvent flashing obtains lithium acetate-coated by titanium dioxide until being evaporated Nickel ion doped.
(2) according to mass ratio 5:95, by lithium acetate-titanium dioxide packet prepared by 0.089g ammonium dihydrogen phosphate and step 1 The nickel ion doped mixing covered is scattered in deionized water, and percent concentration range is 15%.Stirring heating, reacts 4 at 90 DEG C Hour, solution is then dried again, obtains lithium acetate-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped.
(3) lithium acetate-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped that step 2 obtains is put into aluminium oxide In crucible, 700 DEG C are heated under air atmosphere, heating rate is 10 DEG C/min, keeps the temperature 4 hours, then cools to 600 DEG C, is protected Temperature 8 hours, after being cooled to room temperature, obtains positive product.Packed battery after being sliced is taken out, is tested.
Attached drawing 3 is nickel lithium manganate cathode material and the uncoated change after titanium phosphate lithium cladding of embodiment 1-3 preparation Multiplying power test result.As shown, LiTi2(PO4)3Sample after cladding shows outstanding performance under different multiplying.This Show LiTi2(PO4)3Clad helps to improve performance of the material under big multiplying power.Uncoated nickel ion doped sample is at big times The performance declined rapidly under rate is because of active matter under its material and the poor dynamic process of electrolyte interface, and big multiplying power The side reaction of matter and electrolyte destroys the surface texture of material.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow the person skilled in the art to be It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.

Claims (10)

1. a kind of surface coating modification method of nickel lithium manganate cathode material comprising following steps:
(1) mixture: lithium salts 0.1%~5%, alkyl titanate 3%~7%, nickel ion doped 90% is matched according to following mass percent ~95%;First lithium salts and alkyl titanate are dissolved in ethanol solution, nickel ion doped is then added, stirs lower heating, centainly At a temperature of reacted, then solvent flashing obtains lithium salts-coated by titanium dioxide nickel ion doped until being evaporated;
(2) according to mass ratio 0.1:99.9~7:93, by lithium salts-coated by titanium dioxide of ammonium dihydrogen phosphate and step (1) preparation Nickel ion doped mixing be scattered in deionized water, mass percent is 10%~20%, and stirring heating carries out under certain temperature anti- It answers, then dries solution again, obtain lithium salts-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped;
(3) lithium salts-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped that step (2) obtains is put into alumina crucible In, it is heated to 650 ~ 750 DEG C of progress first time heat treatments under air atmosphere, keeps the temperature 3 ~ 8 hours, then cools to 400 ~ 600 DEG C It carries out second to be heat-treated, keeps the temperature 3 ~ 8 hours, after being cooled to room temperature, obtain positive electrode product.
2. method of modifying according to claim 1, which is characterized in that the lithium salts is selected from lithium acetate, lithium carbonate and hydrogen-oxygen Change one of lithium.
3. method of modifying according to claim 1, which is characterized in that the alkyl titanate is butyl titanate.
4. method of modifying according to claim 1, which is characterized in that the preparation side of the nickel ion doped in the step (1) Method are as follows: nickel acetate and manganese acetate are weighed respectively, after deionized water dissolving is added, instill LiOH solution, adjusting pH value is 11-12, Co-precipitation solution heat under 80 °C be concentrated into it is thick, it is dry, grind after, be placed in Muffle furnace 500 °C pre-burning 6 hours, Then cool down the reaction of heat preservation after 650 °C of -900 °C of ranges carry out first heating and heat preservation, and finally cooling obtains nickel acid manganese lithium.
5. method of modifying according to claim 1, which is characterized in that first time heat-treatment temperature range is in step (3) 650~700℃。
6. method of modifying according to claim 1, which is characterized in that second of heat-treatment temperature range is in step (3) 400~500℃。
7. method of modifying according to claim 1, which is characterized in that carry out liter when being heat-treated for the first time in step (3) Warm rate is 2 ~ 10 DEG C/min.
8. a kind of nickel lithium manganate cathode material, which is characterized in that it is prepared by following steps:
(1) mixture: lithium salts 0.1%~5%, alkyl titanate 3%~7%, nickel ion doped 90% is matched according to following mass percent ~95%;First lithium salts and alkyl titanate are dissolved in ethanol solution, nickel ion doped is then added, stirs lower heating, centainly At a temperature of reacted, then solvent flashing obtains lithium salts-coated by titanium dioxide nickel ion doped until being evaporated;
(2) according to mass ratio 0.1:99.9~7:93, by lithium salts-coated by titanium dioxide of ammonium dihydrogen phosphate and step (1) preparation Nickel ion doped mixing be scattered in deionized water, mass percent is 10%~20%, and stirring heating carries out under certain temperature anti- It answers, then dries solution again, obtain lithium salts-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped;
(3) lithium salts-titanium dioxide-ammonium dihydrogen phosphate compound coating nickel ion doped that step (2) obtains is put into alumina crucible In, it is heated to 650 ~ 750 DEG C of progress first time heat treatments under air atmosphere, keeps the temperature 3 ~ 8 hours, then cools to 400 ~ 600 DEG C It carries out second to be heat-treated, keeps the temperature 3 ~ 8 hours, after being cooled to room temperature, obtain positive electrode product.
9. a kind of nickel lithium manganate cathode material according to claim 8, which is characterized in that the lithium salts be selected from lithium acetate, One of lithium carbonate and lithium hydroxide.
10. a kind of electrochemical cell, comprising:
(1) anode,
(2) electrolyte;
(3) cathode;Wherein cathode is made of a kind of anode material for lithium-ion batteries prepared by claim 1 the method;
(4) diaphragm.
CN201610472512.7A 2016-06-24 2016-06-24 A kind of surface coating modification method of nickel lithium manganate cathode material Active CN106025254B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610472512.7A CN106025254B (en) 2016-06-24 2016-06-24 A kind of surface coating modification method of nickel lithium manganate cathode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610472512.7A CN106025254B (en) 2016-06-24 2016-06-24 A kind of surface coating modification method of nickel lithium manganate cathode material

Publications (2)

Publication Number Publication Date
CN106025254A CN106025254A (en) 2016-10-12
CN106025254B true CN106025254B (en) 2019-03-29

Family

ID=57083601

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610472512.7A Active CN106025254B (en) 2016-06-24 2016-06-24 A kind of surface coating modification method of nickel lithium manganate cathode material

Country Status (1)

Country Link
CN (1) CN106025254B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018099754A1 (en) * 2016-11-29 2018-06-07 Basf Se Process for making a coated oxide material, and vessel combination suitable for such process
CN108206276A (en) * 2016-12-19 2018-06-26 天津国安盟固利新材料科技股份有限公司 A kind of lithium ion anode material of compound coating and preparation method thereof
CN107492643A (en) * 2017-07-31 2017-12-19 三峡大学 A kind of titanium phosphate lithium coats LiNi1/3Co1/3Mn1/3O2Positive electrode and preparation method thereof
CN107591529A (en) * 2017-10-10 2018-01-16 中南大学 A kind of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof
CN110776019A (en) * 2018-07-27 2020-02-11 纳米及先进材料研发院有限公司 Synthesis of high-voltage anode material and preparation of high-voltage electrolyte for lithium ion battery
CN109980202A (en) * 2019-03-26 2019-07-05 湖北锂诺新能源科技有限公司 The preparation method of titanium doped and titanium phosphate sodium cladding fluorosulfuric acid ferrous iron lithium anode material
CN112635722B (en) * 2019-10-09 2022-04-15 北京卫蓝新能源科技有限公司 Composite positive electrode material of lithium ion battery and preparation method
CN111987311A (en) * 2020-08-12 2020-11-24 中南大学 Titanium indium lithium phosphate modified positive electrode material and preparation method thereof
CN112194196A (en) * 2020-08-27 2021-01-08 浙江美都海创锂电科技有限公司 Composite coating agent for ultra-high nickel single crystal ternary positive electrode material and preparation method and application thereof
CN114335470B (en) * 2021-12-29 2023-03-10 北京卫蓝新能源科技有限公司 Modified positive electrode material and preparation method and application thereof
CN114843501A (en) * 2022-05-11 2022-08-02 宁波容百新能源科技股份有限公司 Lithium nickel manganese oxide positive electrode material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1930706A (en) * 2004-08-17 2007-03-14 株式会社Lg化学 Lithium secondary batteries with enhanced safety and performance
WO2010051749A1 (en) * 2008-11-05 2010-05-14 Byd Company Limited Method of preparing cathode active material and method of forming lithium secondary battery
CN101969110A (en) * 2010-08-31 2011-02-09 天津巴莫科技股份有限公司 Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1930706A (en) * 2004-08-17 2007-03-14 株式会社Lg化学 Lithium secondary batteries with enhanced safety and performance
WO2010051749A1 (en) * 2008-11-05 2010-05-14 Byd Company Limited Method of preparing cathode active material and method of forming lithium secondary battery
CN101969110A (en) * 2010-08-31 2011-02-09 天津巴莫科技股份有限公司 Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method

Also Published As

Publication number Publication date
CN106025254A (en) 2016-10-12

Similar Documents

Publication Publication Date Title
CN106025254B (en) A kind of surface coating modification method of nickel lithium manganate cathode material
CN101855755B (en) Li-Ni-based composite oxide particle powder for rechargeable battery with nonaqueous elctrolyte, process for producing the powder, and rechargeable battery with nonaqueous electrolyte
CN208797100U (en) A kind of anode pole piece and secondary cell
CN105552344A (en) Positive plate of lithium ion battery, lithium ion battery and preparation method of lithium ion battery
CN101969110A (en) Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method
CN105161693B (en) A kind of high circulation lithium electricity polynary positive pole material NCM and preparation method thereof
CN108390039A (en) A kind of nickelic anode material of lithium battery that double oxide coats altogether and preparation method
CN105244488A (en) Compound cladding positive pole material of lithium ion battery and preparation method of compound cladding positive pole material
CN107403913A (en) A kind of nickel cobalt lithium aluminate cathode material of surface modification and preparation method thereof
CN105932250B (en) A kind of metal-doped spinel structure fast-ionic conductor coats the preparation method and application of nickeliferous positive electrode
Ilango et al. Physical and electrochemical performance of LiNi1/3Co1/3Mn1/3O2 cathodes coated by Sb2O3 using a sol–gel process
CN103474625A (en) Coating method for core-shell novel positive electrode material for lithium ion battery
CN103904305B (en) Negative active core-shell material of a kind of lithium ion battery and preparation method thereof and a kind of lithium ion battery
CN109390553B (en) Composite positive electrode material, positive plate and all-solid-state lithium battery
CN108666558A (en) A kind of bilayer carbon coating prepares the preparation method of lithium vanadium fluorophosphates lithium ionic cell anode material
CN109004212A (en) A kind of big multiplying power manganate cathode material for lithium and preparation method thereof
CN113782715A (en) Preparation method and application of lithium phosphate modified high-nickel cobalt lithium manganate positive electrode material
CN105280910A (en) Phosphorus-contained lithium ion battery positive electrode material and preparation method therefor
CN108899541B (en) Magnesium lithium silicate coated modified lithium zinc titanate negative electrode material and preparation method thereof
Zeng et al. Electrochemical behavior of spherical LiFePO4/C nanomaterial in aqueous electrolyte, and novel aqueous rechargeable lithium battery with LiFePO4/C anode
CN110931774A (en) Composite Ni 65-coated nickel-cobalt-manganese ternary cathode material and preparation method and application thereof
CN103367723A (en) Method for coating nickel cobalt lithium manganate positive-electrode material with calcium fluophosphate
CN103367740A (en) Method for coating nickel cobalt lithium manganate positive-electrode material with calcium fluoride
CN107742722A (en) A kind of method of modifying of lithium ion battery manganate cathode material for lithium
CN103066278A (en) Tin-oxide coated and vanadium-doped lithium iron phosphate material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant