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 PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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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
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.
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| 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 |
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| CN118039872B (en) * | 2024-03-04 | 2024-08-09 | 安徽博石高科新材料股份有限公司 | High-voltage lithium nickel manganese oxide with composite electrolyte membrane on surface and preparation method thereof |
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| 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 |
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2016
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Patent Citations (3)
| 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 |
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