CN109119622A - Lithium-titanium composite oxide, modified lithium titanate material and preparation method thereof, application - Google Patents
Lithium-titanium composite oxide, modified lithium titanate material and preparation method thereof, application Download PDFInfo
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- H—ELECTRICITY
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Abstract
The present invention discloses a kind of lithium-titanium composite oxide, modified lithium titanate material and preparation method thereof, application.The preparation method includes the following steps: the raw mixture of Li source compound and titanium source compound, first after calcining, then carries out surface reduction and handles up to lithium-titanium composite oxide；Wherein, the molar ratio of elemental lithium and titanium elements is b, and 0.75 < b < 0.8 in raw mixture；Surface reduction processing carries out under reducing atmosphere, reducing atmosphere is hydrogen atmosphere or reducing atmosphere is the mixed atmosphere of hydrogen He other gases, other gases are nitrogen and/or inert gas, and the temperature of surface reduction processing is 600-800 DEG C, and the time of surface reduction processing is 5-15h.Lithium titanium compound made from the preparation method has higher ion and electronic conductivity, therefore can reduce the addition of conductive black in battery pole piece manufacturing process, and battery obtained has excellent cycle performance.
Description
Technical field
The present invention relates to a kind of lithium-titanium composite oxides, modified lithium titanate material and preparation method thereof, application.
Background technique
In recent years, spinel type lithium titanate material receives significant attention.Since the material will not be sent out in charge and discharge process
Raw volume change, therefore there is excellent cycle life；In addition, lithium titanate material has high security, this is because with tradition
Carbon negative pole material is compared, which, which has, lower a possibility that Li dendrite occurs；In addition, due to the lithium titanate of spinel structure
For ceramic material, therefore battery does not have the efficiency of thermal diffusion.
However, there is also intrinsic defects for the material: 1) spinel type lithium titanate material ions electric conductivity and electron conduction
It is relatively low, influence battery high rate performance and cycle life；2) material has very strong hygroscopicity, can be during circulating battery
Battery producing gas is caused, while improving the difficulty of material storage process.It is general in view of the above problems all to pass through material surface packet
Coated with and battery pole piece in addition conductive agent improve battery high rate during charging-discharging.Currently, lithium titanate material surface coats
Technology is based on carbon coating and inorganic matter cladding.Wherein, carbon source used in carbon coating includes organic or inorganic carbon source addition, warp
It crosses and produces cladding carbon-coating after Pintsch process on the surface of the material, which can be improved material electronics electric conductivity, while certain
Material is prevented to contact in degree with the direct of electrolyte.Inorganic matter is coated with metal oxide, hydroxide, and fluoride etc. is
It is main.Conductive agent majority is based on super carbon black, acetylene black, carbon nanotube etc. in battery pole piece.
Above-mentioned Pintsch process carbon coating method described in background technology is common skill improved to lithium battery material at present
Art means, however the approach also brings undeniable technical problem while reaching certain technical effect: (1) high anneal crack
Solution is formed by carbon based on amorphous porous carbon, which equally has water imbibition, and is adsorbed in moisture therein subsequent
It is not easy to bake out in use process, battery is easy to flatulence and life time decay；(2) Pintsch process technology production technology is relative complex,
And carbon layers having thicknesses are not easily controlled, and influence batches of materials consistency；(3) the incomplete carbon source surface of Pintsch process has centainly
Functional group is easy to react with electrolyte, causes electrolyte failure and battery life decaying.
The means of battery pole piece electric conductivity are made up in addition, adding plentiful conductive black in the battery although and being, but this
A little charcoal substances itself can not form stable SEI film, and the active site on its surface is easy to react and generate with electrolyte
A large amount of gas, causes circulating battery to be destroyed.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome existing Pintsch process carbon coating method to be formed by nothing
There is setting porous carbon water imbibition to be not easy to bake out in subsequent use process, Pintsch process technology production technology is relative complex,
Carbon layers having thicknesses are not easily controlled and then influence batches of materials consistency, and Pintsch process not exclusively influences material property,
Conductive black is added in battery can not form stable SEI film, the active site on its surface is made to be easy to occur instead with electrolyte
It answers and generates a large amount of gas and then cause circulating battery by the defect destroyed, and a kind of novel lithium titanium combined oxidation is provided
Object, modified lithium titanate material and preparation method thereof, application.
The present invention solves above-mentioned technical problem by the following technical programs:
The present invention provides a kind of preparation method of lithium-titanium composite oxide, and the preparation method includes the following steps: lithium source
The raw mixture of compound and titanium source compound first after calcining, then carries out surface reduction and handles up to lithium titanium combined oxidation
Object；Wherein, the molar ratio of elemental lithium and titanium elements is b, and 0.75 < b < 0.8 in the raw mixture；The surface reduction
Processing carries out under reducing atmosphere, and the reducing atmosphere is hydrogen atmosphere or the reducing atmosphere is hydrogen and other gases
Mixed atmosphere, other described gases are nitrogen and/or inert gas, and the temperature of the surface reduction processing is 600-800 DEG C, institute
The time for stating surface reduction processing is 5-15h.
In the preparation method of above-mentioned lithium-titanium composite oxide, the b may be, for example, 0.789.
In the preparation method of above-mentioned lithium-titanium composite oxide, the Li source compound can be lithium source commonly used in the art
Compound, the Li source compound are preferably lithium carbonate and/or lithium hydroxide.
In the preparation method of above-mentioned lithium-titanium composite oxide, the titanium source compound can be titanium source commonly used in the art
Compound, the titanium source compound are preferably titanium dioxide.
In the preparation method of above-mentioned lithium-titanium composite oxide, pre-burning is preferably passed through before the calcining, the pre-burning is pressed
This field routinely carries out under air atmosphere or oxygen atmosphere.The temperature of the pre-burning is preferably 350-650 DEG C.The pre-burning
Time is preferably 3-5h.
In the preparation method of above-mentioned lithium-titanium composite oxide, the method and condition of the calcining can be the side of this field routine
Method and condition, for example, the calcining carries out under air atmosphere or oxygen atmosphere by this field is conventional.The temperature of the calcining compared with
It goodly is 700-900 DEG C.The time of the calcining is preferably 5-15h.
In the preparation method of above-mentioned lithium-titanium composite oxide, the reducing atmosphere is preferably hydrogen and other described gases
Mixed atmosphere.Other described gases are preferably argon gas.The mass ratio of hydrogen and other gases in the reducing atmosphere
Preferably 5:95.
In the preparation method of above-mentioned lithium-titanium composite oxide, preferably, the lithium-titanium composite oxide includes that lithium titanizing is closed
Object and indefinite phase oxidation titanium, the molecular formula of the lithium titanium compound are LixMaTi5-aOc, wherein what M was referred to is dopant, and x is
3.95-4.05, a 0.01-0.02, c 11.5-12.5；The molecular formula of the indefinite phase oxidation titanium is TimOn, wherein 0 < m
≤ 1,1≤n≤2；The mass fraction of indefinite phase oxidation titanium described in the lithium-titanium composite oxide is w, and 0 < w≤20%.More
Goodly, the dopant is one of Mg, Al, Fe, Zr, Nb, Cd, Ca and K or a variety of.
In the preparation method of above-mentioned lithium-titanium composite oxide, the lithium titanium compound can be spinel structure or ramsdellite
Structure, preferably spinel structure.
In the preparation method of above-mentioned lithium-titanium composite oxide, the indefinite phase oxidation titanium can be Rutile structure or rutile titania
Mine type structure, preferably Detitanium-ore-type structure.
The present invention also provides the lithium titanium composite oxygens made from a kind of preparation method as lithium-titanium composite oxide above-mentioned
Compound.
The present invention also provides a kind of preparation method of modified lithium titanate material, the preparation method include the following steps: by
Lithium-titanium composite oxide and hydrophobic conductive high-molecular compound monomer above-mentioned is in water phase and/or the mixed system of oily phase composition
In, the polymerization reaction of surface high-molecular compound is carried out up to modified lithium titanate material；In the modified lithium titanate material, by institute
State the ratio of the quality of the clad of hydrophobic conductive high-molecular compound monomer formation and the quality of the lithium-titanium composite oxide
Value is 0.5%-10%
In the preparation method of above-mentioned modified lithium titanate material, preferably, being handled after the polymerization reaction without cracking.
The lithium-titanium composite oxide can effectively prevent lithium titanium multiple after hydrophobic conductive high-molecular compound monomer cladding
Oxide is closed to contact with the direct of moisture, since the electric conductivity of hydrophobic conductive high-molecular compound monomer is fabulous, therefore can be into one
Step reduces the water imbibition of gained lithium titanate material, so that gained lithium titanate material has very strong hydrophobic property, and this is hydrophobic
Characteristic guarantees hydrophobic properties of the lithium titanate material in storage and use process, easy to process.
The preparation method of the modified lithium titanate material, can be real according to the additional amount of hydrophobic conductive high-molecular compound monomer
Now the controllability of coating thickness is adjusted, and makes gained coating thickness uniform.
The preparation method of the modified lithium titanate material, polymerization reaction do not need Pintsch process processing later, eliminate tradition
Pyrolysis step in carbon coating method, therefore simple process.
In the preparation method of above-mentioned modified lithium titanate material, the hydrophobic conductive high-molecular compound monomer can be existing
There is hydrophobicity, electric conductivity and the high-molecular compound monomer that the polymerization reaction can occur in technology.The hydrophobicity
Conducting polymer compound monomer is preferably aniline, vinylpyrrolidone, ethylene glycol, acrylonitrile, styrene, vinylpyridine
It coughs up, one of acrylic acid and vinylidene or a variety of, is more preferably aniline, vinylpyrrolidone, ethylene glycol, acrylonitrile, benzene
Ethylene, vinyl pyrrole, acrylic acid or vinylidene.
In the preparation method of above-mentioned modified lithium titanate material, the oil mutually can be not influence the hydrophobic conductive macromolecule
The organic solvent of the polymerization reaction occurs for compound monomer.It is described oil mutually be preferably N-Methyl pyrrolidone, tetrahydrofuran,
One of ethers and sulfone class are a variety of, are more preferably N-Methyl pyrrolidone or ether.
In the preparation method of above-mentioned modified lithium titanate material, preferably, the time of the polymerization reaction is 0.5-5h.
In the preparation method of above-mentioned modified lithium titanate material, preferably, the polymerization reaction carries out under stiring.
In the preparation method of above-mentioned modified lithium titanate material, it can be filtered and be dried after the polymerization reaction.The baking
Dry temperature is preferably 150-300 DEG C.
In a preferred embodiment of the invention, the preparation method of the modified lithium titanate material includes the following steps: lithium
The raw mixture of source compound and titanium source compound first after pre-burning and calcining, then carries out surface reduction and handles up to lithium titanium
Composite oxides；By the lithium-titanium composite oxide in water phase and/or the mixed system of oily phase composition, surface macromolecule is carried out
The polymerization reaction of compound is up to modified lithium titanate material；
Wherein, the atmosphere of the pre-burning, temperature and time are respectively air atmosphere, 500 DEG C and 5h, the gas of the calcining
Atmosphere, temperature and time are respectively air atmosphere, 700 DEG C and 10h, and the atmosphere of the surface reduction processing is 95wt%'s and 5%
The temperature and time of the atmosphere of argon gas and hydrogen composition, the surface reduction processing is respectively 650 DEG C and 5h, and the lithium titanium is compound
Oxide contains the Li of 90wt%4Ti4.97K0.03O12With the TiO of 10wt%2；
Wherein, the hydrophobic conductive high-molecular compound monomer is aniline, in the modified lithium titanate material, by described
The ratio of the quality of the quality and lithium-titanium composite oxide for the clad that hydrophobic conductive high-molecular compound monomer is formed
It is 5%；Wherein handled after the cladding without cracking.
In the preparation method of above-mentioned modified lithium titanate material, the temperature of the cracking processing is typically larger than 300 DEG C.
The present invention also provides modified lithium titanate materials made from a kind of preparation method as modified lithium titanate material above-mentioned.
The present invention also provides a kind of modified lithium titanate materials above-mentioned to prepare the application in battery.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can any combination to get the present invention it is each preferably
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
Lithium-titanium composite oxide made from preparation method through the invention is by lithium titanium compound and indefinite phase oxidation titanium group
At, and lithium titanium compound is spinel structure or ramsdellite structure, indefinite phase oxidation titanium is the golden red of lattice atoms modified
Stone-type structure or Detitanium-ore-type structure.Meanwhile indefinite phase oxidation titanium made from the preparation method, there is relatively low water suction
Property, therefore can improve the stronger defect of material hygroscopicity itself the problem of so as to improve battery producing gas and circulation, and improves material
The processing performance of material.
With lithium titanate material (the structural formula Li of existing spinel structure4Ti5O12) compare, preparation method of the invention
Lithium titanium compound obtained has higher ion and electronic conductivity, therefore can reduce conductive charcoal in battery pole piece manufacturing process
Black addition, and battery obtained has excellent cycle performance.
Detailed description of the invention
Fig. 1 is the structure schematic drawing of modified lithium titanate material obtained by embodiment 2-7.
Fig. 2 is the TEM photo of the lithium-titanium composite oxide of embodiment 1.
Fig. 3 is the result of the hydrophobicity analysis of the modified lithium titanate material of embodiment 2 and the lithium titanate material of comparative example 1
Figure.
Fig. 4 is the stereoscan photograph of 3 gained modified lithium titanate material of embodiment.
Fig. 5 is the circulation of 3 gained lithium titanate material of 4 gained modified lithium titanate material of embodiment and comparative example 2 and comparative example
Performance map.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiments, the definition of covering amount is in the modified lithium titanate material by hydrophobic conductive macromolecule chemical combination
The ratio of the quality of the quality and lithium-titanium composite oxide for the clad that object monomer is formed.
Embodiment 1
By lithium carbonate, titanium dioxide, dopant according to Li can be made4Ti4.97K0.03O12+ 10%TiO2Lithium titanium composite oxygen
Compound (refers in the lithium-titanium composite oxide, TiO2Molar fraction account for Li4Ti4.97K0.03O12The ratio of molar fraction be
10%) proportion carries out raw material mixing, and in air atmosphere, the pre-burning 5h at 500 DEG C, calcines 10h at 700 DEG C, in hydrogen respectively
Reducing atmosphere (wherein, the mass ratio of argon gas and hydrogen is 95:5) lower 650 DEG C of surface reductions of gas and argon gas handle 5h to get lithium
Titanium composite oxide.
Technical effect: the TEM of gained lithium-titanium composite oxide is as shown in Fig. 2, this it appears that two groups different from Fig. 2
Selection lattice diffraction fringe, be spinel-type Li respectively4Ti4.97K0.03O12With Detitanium-ore-type TiO2。
Embodiment 2
By 1 gained lithium-titanium composite oxide of embodiment, dispersed in oil-based system N-Methyl pyrrolidone, is slowly added
Enter aniline monomer, stir 3h, carries out the polymerization reaction of surface high-molecular compound to get modified lithium titanate material, covering amount point
Not Wei 1%, 2%, 3%, to gained modified lithium titanate material carry out hydrophobicity test, as a result as shown in Figure 3.In Fig. 3, GZ13,
The covering amount of GZ12, GZ11 are respectively 1%, 2%, 3%.
Comparative example 1
By the Li of this field routine4Ti5O12Synthetic method be made comparative example 1 Li4Ti5O12Material, specific synthetic method
Are as follows: lithium salts mixes sand milling with titanium source liquid phase, and spray drying is sintered to get Li4Ti5O12Material, number GZ01.
Herein, it should be noted that inventor has found that GZ01 is not due to carrying out Ti in the course of the researchmOnIt is modified, it is difficult
Carry out the polymerization reaction of surface high-molecular compound as described in Example 2.
The hydrophobicity result of the lithium titanate material of the modified lithium titanate material and comparative example 1 of 1 embodiment 2 of table
From being can be seen that in table 1 and Fig. 3 when covering amount is within the scope of 1%-3%, with the increase of covering amount, contact
Angle is bigger namely hydrophobicity is better.The embodiment can valid certificates hydrophobic polymer material in lithium-titanium composite oxide table
The interface interaction in face.
Embodiment 3
By 1 gained lithium-titanium composite oxide of embodiment, is dispersed in oil-based system ether, be slowly added to ethylene pyrroles
Alkanone monomer stirs 5h, carries out the polymerization reaction of surface high-molecular compound to get modified lithium titanate material, covering amount is
1.5%.Electron microscope analysis is scanned to gained modified lithium titanate material, as a result as shown in Figure 4.
Technical effect: from fig. 4, it can be seen that the surface of gained modified lithium titanate material has clearly high molecular material side
Boundary.
Embodiment 4
By 1 gained lithium-titanium composite oxide of embodiment, is dispersed in aqueous phase system, be slowly added to aniline monomer, stirred
5h is mixed, modified lithium titanate material of the polymerization reaction of surface high-molecular compound to get structure as shown in Figure 1, covering amount are carried out
It is 5%, electrochemical property test is carried out to gained modified lithium titanate material, as a result as shown in Figure 5.
Comparative example 2
1 gained lithium-titanium composite oxide of embodiment is directly subjected to electrification without cladding (namely covering amount is 0%)
Performance test is learned, as a result as shown in Figure 5.
Comparative example 3
By 1 gained lithium-titanium composite oxide of embodiment, is dispersed in aqueous phase system, be slowly added to aniline monomer, stirred
5h is mixed, carries out the polymerization reaction of surface high-molecular compound to get modified lithium titanate material, covering amount 15% changes gained
Property lithium titanate material carry out electrochemical property test, as a result as shown in Figure 5.
Embodiment 4 and comparative example 2 and comparative example 3 carry out resulting materials to be button electricity used by electrochemical property test
Battery pole piece, diaphragm and lithium piece are put into button cell steel shell by pond in a certain order, are instilled electrolyte, are utilized buckle closure
Machine seals battery case, and make-up electricity carries out the cycle performance of 0.2C, 2C, 4C, 0.2C multiplying power in blue electrical measurement test system after standing
Test.
From figure 5 it can be seen that gained modified lithium titanate material shows optimal cyclicity when covering amount is 5%
Energy.It can be seen that cladding polyaniline can be effectively improved the electrochemical behavior of lithium-titanium composite oxide.However, when covering amount reaches
When to 15%, the cycle performance of gained modified lithium titanate material is declined, it can be seen that, clad is thicker, can inhibit material
The performance of performance.
The electrochemical performance data of 2 embodiment 4 of table and comparative example 2-3 gained lithium titanate material
Embodiment 5-7
Modified lithium titanate material obtained by embodiment 5-7 uses test method same as Example 4, the circulation of gained battery
Performance and embodiment 4 are suitable.
Although specific embodiments of the present invention have been described above, it will be appreciated by those of skill in the art that this is only
For example, protection scope of the present invention is to be defined by the appended claims.Those skilled in the art without departing substantially from
Under the premise of the principle and substance of the present invention, many changes and modifications may be made, but these change and
Modification each falls within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of lithium-titanium composite oxide, which is characterized in that the preparation method includes the following steps: lithium source
The raw mixture for closing object and titanium source compound first after calcining, then carries out surface reduction and handles up to lithium-titanium composite oxide；
Wherein, the molar ratio of elemental lithium and titanium elements is b, and 0.75 < b < 0.8 in the raw mixture；At the surface reduction
Reason carries out under reducing atmosphere, and the reducing atmosphere is hydrogen atmosphere or the reducing atmosphere is the mixed of hydrogen and other gases
Atmosphere is closed, other described gases are nitrogen and/or inert gas, and the temperature of the surface reduction processing is 600-800 DEG C, described
The time of surface reduction processing is 5-15h.
2. the preparation method of lithium-titanium composite oxide as described in claim 1, which is characterized in that the Li source compound is carbon
Sour lithium and/or lithium hydroxide；
And/or the titanium source compound is titanium dioxide.
3. the preparation method of lithium-titanium composite oxide as described in claim 1, which is characterized in that by pre- before the calcining
It burns, the pre-burning carries out under air atmosphere or oxygen atmosphere；Wherein, the temperature of the pre-burning is preferably 350-650 DEG C；Institute
It states burn-in time and is preferably 3-5h；
And/or the calcining carries out under air atmosphere or oxygen atmosphere；Wherein, the temperature of the calcining is preferably 700-
900℃；The time of the calcining is preferably 5-15h；
And/or the reducing atmosphere is the mixed atmosphere of hydrogen and other gases；Wherein, other described gases are preferably
For argon gas；The mass ratio of hydrogen and other gases is preferably 5:95 in the reducing atmosphere.
4. the preparation method of lithium-titanium composite oxide as described in claim 1, which is characterized in that the lithium-titanium composite oxide
Including lithium titanium compound and indefinite phase oxidation titanium, the molecular formula of the lithium titanium compound is LixMaTi5-aOc, wherein what M was referred to
It is dopant, x 3.95-4.05, a 0.01-0.02, c 11.5-12.5；The molecular formula of the indefinite phase oxidation titanium is
TimOn, wherein 0 < m≤1,1≤n≤2；The mass fraction of indefinite phase oxidation titanium described in the lithium-titanium composite oxide is w,
And 0 < w≤20%；Wherein, the dopant is preferably one of Mg, Al, Fe, Zr, Nb, Cd, Ca and K or a variety of.
5. the preparation method of lithium-titanium composite oxide as claimed in claim 4, which is characterized in that the lithium titanium compound is point
Spinel structure or ramsdellite structure, preferably spinel structure；
And/or the indefinite phase oxidation titanium is Rutile structure or Detitanium-ore-type structure, preferably Detitanium-ore-type structure.
6. the lithium titanium made from a kind of preparation method as lithium-titanium composite oxide as described in any one in claim 1-5 is answered
Close oxide.
7. a kind of preparation method of modified lithium titanate material, which is characterized in that the preparation method includes the following steps: such as to weigh
Benefit require 6 described in lithium-titanium composite oxide and hydrophobic conductive high-molecular compound monomer in water phase and/or oily phase composition
In mixed system, the polymerization reaction of surface high-molecular compound is carried out up to modified lithium titanate material；The modified lithium titanate material
In material, the quality of the clad formed by the hydrophobic conductive high-molecular compound monomer and the lithium-titanium composite oxide
The ratio of quality is 0.5%-10%；Wherein, preferably, being handled after the polymerization reaction without cracking.
8. the preparation method of modified lithium titanate material as claimed in claim 7, which is characterized in that the hydrophobic conductive high score
Sub- compound monomer is aniline, vinylpyrrolidone, ethylene glycol, acrylonitrile, styrene, vinyl pyrrole, acrylic acid and inclined fluorine
One of ethylene is a variety of, preferably aniline, vinylpyrrolidone, ethylene glycol, acrylonitrile, styrene, vinyl pyrrole,
Acrylic acid or vinylidene；
And/or the oil is mutually one of N-Methyl pyrrolidone, tetrahydrofuran, ethers and sulfone class or a variety of, preferably
N-Methyl pyrrolidone or ether；
And/or the time of the polymerization reaction is 0.5-5h；
And/or the polymerization reaction carries out under stiring；
And/or it is filtered and is dried after the polymerization reaction；Wherein, the temperature of the drying is preferably 150-300 DEG C.
9. the modified lithium titanate made from a kind of preparation method as modified lithium titanate material as claimed in claim 7 or 8
Material.
10. a kind of modified lithium titanate material as claimed in claim 9 is preparing the application in battery.
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| CN116119726A (en) * | 2023-04-20 | 2023-05-16 | 江苏正力新能电池技术有限公司 | Modified lithium ion negative electrode material, preparation and application thereof |
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| CN101364642A (en) * | 2007-08-10 | 2009-02-11 | 株式会社东芝 | Active material for battery, manufacturing method of the same, non-aqueous electrolytic battery and battery pack |
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| CN101364642A (en) * | 2007-08-10 | 2009-02-11 | 株式会社东芝 | Active material for battery, manufacturing method of the same, non-aqueous electrolytic battery and battery pack |
| CN102569767A (en) * | 2012-01-19 | 2012-07-11 | 中国科学院过程工程研究所 | Polymer composite lithium titanate electrode material and preparation method thereof |
| CN107324379A (en) * | 2017-06-30 | 2017-11-07 | 江苏特丰新材料科技有限公司 | A kind of high power capacity lithium titanate material preparation method |
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| CN116119726A (en) * | 2023-04-20 | 2023-05-16 | 江苏正力新能电池技术有限公司 | Modified lithium ion negative electrode material, preparation and application thereof |
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