CN106532031A - Li4Ti5O12 negative material and lithium titanate battery prepared from same - Google Patents
Li4Ti5O12 negative material and lithium titanate battery prepared from same Download PDFInfo
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- CN106532031A CN106532031A CN201710011377.0A CN201710011377A CN106532031A CN 106532031 A CN106532031 A CN 106532031A CN 201710011377 A CN201710011377 A CN 201710011377A CN 106532031 A CN106532031 A CN 106532031A
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—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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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to an Li4Ti5O12 negative material and a lithium titanate battery prepared the Li4Ti5O12 negative material. The Li4Ti5O12 negative material disclosed by the invention is of a multilayer core-shell structure, and is prepared from an Li4Ti5O12 material in the center, an Li1+2xM2yTi(2-x-y)P3O12-x layer in the middle and a conducting carbon layer on the surface, wherein x and y are in the range of 0 to 0.2. The lithium titanate battery is prepared from an active substance using the Li4Ti5O12 material as a negative plate. The Li4Ti5O12 negative material and the lithium titanate battery disclosed by the invention have excellent electrochemical performance, cycling stability and safety, and are expected to be widely applied in the fields of new energy automobiles and energy storage.
Description
Technical field
The present invention relates to a kind of Li4Ti5O12The preparation work of negative material, negative electrode for lithium ion battery and lithium ion battery
Skill.Belong to technical field of electrochemistry.
Background technology
With the progress of science and technology, electronic product, electric tool, mobile product more and more occur in the life of people
In.The fast development of these products needs high performance battery.Wherein lithium ion battery is relative to lead-acid accumulator, NI-G electricity
Pond, Ni-MH battery have the advantages that high running voltage, high specific energy, therefore obtain a wide range of applications.
Lithium titanate (Li4Ti5O12) with spinel structure, is the negative material of a kind of " zero strain ", and discharge voltage is put down
Surely, intercalation potential height (vs.1.55V), is difficult to cause lithium metal to separate out, and material source is wide, clean environment firendly.Using lithium titanate conduct
The battery of negative pole, with excellent cycle life, is expected to be widely used in new-energy automobile and energy storage field.But
The electronic conductivity of lithium titanate material is low so that battery capacity attenuation during high rate charge-discharge is very fast.Simultaneously by metatitanic acid
Battery prepared by lithium material in cyclic process, especially at high temperature, battery can aerogenesis to a certain extent, cause battery swollen
It is swollen, affect which to use.Its reason be lithium titanate in embedding lithium state with stronger reproducibility.Lived using lithium titanate as anode
The lithium ion battery of property material, is usually used the electrolyte close with the battery with graphite as anode, such as application number
200810052728.3 Chinese patent, the lithium ion battery with lithium titanate as anode, the solute of its electrolyte is hexafluorophosphoric acid
Lithium, multicomponent mixture of the solvent for vinyl carbonate, dimethyl carbonate and ethyl methyl carbonate.And result of study shows,
The solvent of battery electrolyte is easy to reduction reaction on metatitanic acid lithium electrode, especially reacts in high temperature and becomes apparent from.
Coating technology is that the modified important channel of chemical property, particularly carbon bag are carried out to lithium titanate (Li4Ti5O12)
Coating technique.The Chinese patent of such as application number 201010261934.2 discloses a kind of preparation method of carbon coating lithium titanate.Carbon
Although cladding can significantly improve material electronics electrical conductivity, to lithium titanate (Li4Ti5O12) as negative electrode active material
Lithium ion battery aerogenesis phenomenon does not have too big effect.Limit the further use of lithium titanate battery.
The content of the invention
It is an object of the invention to provide a kind of Li4Ti5O12Negative material and its made by lithium titanate battery, solve it is existing
The not good problem of filler scavenging effect in technology.
To achieve these goals, the technical solution used in the present invention is as follows：
The Li of the present invention4Ti5O12The technical scheme of negative material is to lithium titanate (Li by coating technology4Ti5O12) carry out
Multilayer coating structure.So that Li4Ti5O12Negative material has the nucleocapsid structure of multilamellar, its Li by center4Ti5O12Material, it is middle
Li1+2xM2yTi(2-x-y)P3O12-xThe conductive carbon layer on (wherein x, y are 0～0.2) layer and surface is constituted.Wherein there is high ion-conductance
Conductance and low electronic conductivity Li1+2xM2yTi(2-x-y)P3O12-xLayer can effectively suppress the solvent molecule in electrolyte in titanium
Reduction reaction on sour lithium electrode.Lithium titanate battery is by multi-layer core-shell structure Li4Ti5O12Material is as negative plate preparation
Into.
Specifically include following steps：
A, by the compound of Li source compound, titanium dioxide, P source compound and doped chemical M, stoichiometrically claim
Amount；
B, by the powder body material and liquid in step A according to mass ratio be 1：10～1：50 weigh deionized water, ethanol or
Acetone is used as dispersant；Stirring and drying after ball milling mixing is uniform；
C, dried powder body in step B is placed in Muffle furnace, it is little in 800 DEG C～1200 DEG C roasting temperatures 6～20
When, natural cooling obtains required powder body material；
D, the powder body material by step C, carbon source and deionized water are 1 according to mass ratio：0.1：10～1：0.25：50 claim
Stirring and drying after amount ball milling mixing is uniform；
E, dried powder body in step D is placed in nitrogen atmosphere protection stove, in 500 DEG C～750 DEG C roasting temperatures 2
～6 hours, natural cooling obtained final Li4Ti5O12Negative material.
Heretofore described Li source compound selected from Lithium hydrate, lithium carbonate, lithium oxalate, lithium acetate, lithium dihydrogen phosphate,
Any one in lithium nitrate or Quilonorm (SKB)；The compound of described doped chemical M is the oxide of Mg, Sc, Al, hydroxide or
Any one of carbonate；Described P source compound is in lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium phosphate or ammonium phosphate
Any one；Described carbon source be Tween 80, polysorbate60, any one in polysorbate40.
The lithium titanate battery technical scheme of the present invention is as follows：
A kind of lithium titanate battery, including positive pole, negative pole, barrier film and electrolyte.The work of negative plate used by lithium titanate battery
Property material is above-mentioned Li4Ti5O12Material；The active substance of positive plate used is cobalt acid lithium (LiCoO2), LiMn2O4
(LiMn2O4), one or more in nickle cobalt lithium manganate and nickel cobalt lithium aluminate.
The present invention compared with prior art, with advantages below and beneficial effect：
The Li of the multi-layer core-shell structure prepared by the present invention4Ti5O12Material structure is stable, even particle size, material electricity
Conductance is high, and removal lithium embedded reversibility is good, and big high rate performance is excellent.There is high ionic conductivity and low electronic conductivity simultaneously
Li1+2xM2yTi(2-x-y)P3O12-xLayer can reduce electrolyte and Li4Ti5O12Directly contact, in effectively suppressing electrolyte
Reduction reaction of the solvent molecule on metatitanic acid lithium electrode so that the lithium titanate battery prepared using the material possesses good high temperature
Cyclical stability and safety.
Description of the drawings
Fig. 1 is the Li of multi-layer core-shell structure in embodiment 14Ti5O12The TEM photos of material.
Fig. 2 is lithium titanate battery internal structure schematic diagram in embodiment 1.
Fig. 3 is the high temperature cyclic performance collection of illustrative plates of lithium titanate battery in embodiment 1.
Specific embodiment
With reference to embodiment, the invention will be further described, and embodiments of the present invention include but is not limited to following reality
Apply example.
Embodiment 1
Li used by the lithium titanate battery of the present embodiment4Ti5O12Negative material, concrete composition are Li4Ti5O12For 96 parts,
Li1+2xM2yTi(2-x-y)P3O12-x(x=0.1, y=0.1, M=Mg) is 3 parts, 1 part of carbon-coating.Li4Ti5O12Negative material.Prepare step
It is rapid as follows：
First by lithium carbonate, titanium dioxide, ammonium dihydrogen phosphate and magnesium carbonate, stoichiometrically weigh.Secondly will weigh
Powder body material and deionized water be 1 according to mass ratio：Slurry agitation is dried after ball milling mixing is uniform by 10 ball milling mixings.Dry
Powder body after dry is placed in Muffle furnace, and in 980 DEG C of roasting temperatures 12 hours, natural cooling obtained Li4Ti5O12/
Li1.2Mg0.2Ti1.8P3O11.9Powder body material.By Li4Ti5O12/Li1.2Mg0.2Ti1.8P3O11.9Powder body, Tween 80, deionized water are pressed
It is 1 according to mass ratio：0.25：10 weigh the uniform rear stirring and drying of ball milling mixing.The last dried powder body of previous step is placed in nitrogen
In gas atmosphere protection stove, in 600 DEG C of roasting temperatures 6 hours, natural cooling obtained final Li4Ti5O12/
Li1.2Mg0.2Ti1.8P3O11.9/ C negative materials.Fig. 1 gives the TEM photos of the material.
The lithium titanate battery of the present embodiment, as shown in Fig. 2 including positive plate, negative plate and barrier film, negative plate is by negative pole collection
Fluid aluminium foil and the Li being coated on negative current collector4Ti5O12/Li1.2Mg0.2Ti1.8P3O11.9/ C layers are constituted.Positive plate is by positive pole
Current collector aluminum foil and the anode material nickel cobalt manganic acid lithium layer being coated on plus plate current-collecting body are constituted.Positive plate and negative plate adopt phase
Mutually staggeredly the mode of lamination is assembled, and the area of negative plate is more than the area of positive plate, can make negative plate by positive plate
Cover.
Fig. 3 gives the high temperature cyclic performance figure of lithium titanate battery in the present embodiment.Method of testing is：It is positioned over calorstat
In make charge and discharge cycles test.Calorstat temperature is kept for 45 DEG C, and charge and discharge cycles voltage range 2.9-1.5V, charging and discharging currents are equal
For 20A, the time of repose that discharge and recharge is changed is 10 minutes.Resulting battery capacity attenuation curve is as shown in Figure 3：Prepared
Lithium manganate battery high temperature circulation excellent in stability.
Embodiment 2
Li used by the lithium titanate battery of the present embodiment4Ti5O12Negative material, concrete composition are Li4Ti5O12For 98 parts,
Li1+2xM2yTi(2-x-y)P3O12-x(x=0.1, y=0.1, M=Mg) is 2 parts, 0.1 part of carbon-coating.Li4Ti5O12Negative material.Prepare
Step is as follows：
First by Lithium hydrate, titanium dioxide, ammonium hydrogen phosphate and magnesium carbonate, stoichiometrically weigh.Secondly will weigh
Powder body material and deionized water be 1 according to mass ratio：Slurry agitation is dried after ball milling mixing is uniform by 50 ball milling mixings.Dry
Powder body after dry is placed in Muffle furnace, and in 800 DEG C of roasting temperatures 20 hours, natural cooling obtained Li4Ti5O12/
Li1.2Mg0.2Ti1.8P3O11.9Powder body material.By Li4Ti5O12/Li1.2Mg0.2Ti1.8P3O11.9Powder body, polysorbate60, deionized water are pressed
It is 1 according to mass ratio：0.25：50 weigh the uniform rear stirring and drying of ball milling mixing.The last dried powder body of previous step is placed in nitrogen
In gas atmosphere protection stove, in 500 DEG C of roasting temperatures 6 hours, natural cooling obtained final Li4Ti5O12/
Li1.2Mg0.2Ti1.8P3O11.9/ C negative materials.
The lithium titanate battery of the present embodiment, including positive plate, negative plate and barrier film, negative plate by negative current collector aluminium foil and
The Li being coated on negative current collector4Ti5O12/Li1.2Mg0.2Ti1.8P3O11.9/ C layers are constituted.Positive plate is by plus plate current-collecting body aluminium foil
Constitute with the positive-material lithium manganate and nickle cobalt lithium manganate layer being coated on plus plate current-collecting body.Positive plate and negative plate are using mutual
Staggeredly the mode of lamination is assembled, and the area of negative plate is more than the area of positive plate, can make negative plate by positive plate lid
Firmly.
Embodiment 3
Li used by the lithium titanate battery of the present embodiment4Ti5O12Negative material, concrete composition are Li4Ti5O12For 95 parts,
Li1+2xM2yTi(2-x-y)P3O12-x(x=0.1, y=0.2, M=Al) is 4 parts, 0.1 part of carbon-coating.Li4Ti5O12Negative material.Prepare
Step is as follows：
First by Lithium hydrate, titanium dioxide, ammonium hydrogen phosphate and aluminium oxide, stoichiometrically weigh.Secondly will weigh
Powder body material and deionized water be 1 according to mass ratio：Slurry agitation is dried after ball milling mixing is uniform by 50 ball milling mixings.Dry
Powder body after dry is placed in Muffle furnace, and in 1200 DEG C of roasting temperatures 6 hours, natural cooling obtained Li4Ti5O12/
Li1.2Al0.4Ti1.6P3O11.9Powder body material.By Li4Ti5O12/Li1.2Al0.2Ti1.8P3O11.9Powder body, polysorbate60, deionized water are pressed
It is 1 according to mass ratio：0.25：50 weigh the uniform rear stirring and drying of ball milling mixing.The last dried powder body of previous step is placed in nitrogen
In gas atmosphere protection stove, in 500 DEG C of roasting temperatures 6 hours, natural cooling obtained final Li4Ti5O12/
Li1.2Al0.2Ti1.8P3O11.9/ C negative materials.
The lithium titanate battery of the present embodiment, including positive plate, negative plate and barrier film, negative plate by negative current collector aluminium foil and
The Li being coated on negative current collector4Ti5O12/Li1.2Al0.2Ti1.8P3O11.9/ C layers are constituted.Positive plate is by plus plate current-collecting body aluminium foil
Constitute with the positive-material lithium manganate layer being coated on plus plate current-collecting body.Positive plate and negative plate adopt the side of interlaced lamination
Formula is assembled, and the area of negative plate is more than the area of positive plate, so that negative plate can be made to cover positive plate.
Embodiment 4
Li used by the lithium titanate battery of the present embodiment4Ti5O12Negative material, concrete composition are Li4Ti5O12For 97 parts,
Li1+2xM2yTi(2-x-y)P3O12-x(x=0, y=0.2, M=Sc) is 2 parts, 1 part of carbon-coating.Li4Ti5O12Negative material.Preparation process
It is as follows：
First by lithium carbonate, titanium dioxide, ammonium phosphate and strontium oxide, stoichiometrically weigh.Secondly the powder that will be weighed
Body material and deionized water are 1 according to mass ratio：Slurry agitation is dried after ball milling mixing is uniform by 50 ball milling mixings.After drying
Powder body be placed in Muffle furnace, in 800 DEG C of roasting temperatures 20 hours, natural cooling obtained Li4Ti5O12/
Li1Sr0.4Ti1.8P3O12Powder body material.By Li4Ti5O12/Li1Sr0.4Ti1.8P3O12Powder body, polysorbate40, deionized water are according to quality
Than for 1：0.1：10 weigh the uniform rear stirring and drying of ball milling mixing.The last dried powder body of previous step is placed in nitrogen atmosphere guarantor
In furnace retaining, in 750 DEG C of roasting temperatures 2 hours, natural cooling obtained final Li4Ti5O12/Li1Sr0.4Ti1.8P3O12/ C negative poles
Material.
The lithium titanate battery of the present embodiment, including positive plate, negative plate and barrier film, negative plate by negative current collector aluminium foil and
The Li being coated on negative current collector4Ti5O12/Li1Sr0.4Ti1.8P3O12/ C layers are constituted.Positive plate by plus plate current-collecting body aluminium foil and
The anode material nickel cobalt aluminic acid lithium layer being coated on plus plate current-collecting body is constituted.Positive plate and negative plate are using interlaced lamination
Mode is assembled, and the area of negative plate is more than the area of positive plate, so that negative plate can be made to cover positive plate.
Embodiment 5
Li used by the lithium titanate battery of the present embodiment4Ti5O12Negative material, concrete composition are Li4Ti5O12For 97 parts,
Li1+2xM2yTi(2-x-y)P3O12-x(x=0, y=0) is 2 parts, 1 part of carbon-coating.Li4Ti5O12Negative material.Preparation process is as follows：
First by lithium carbonate, titanium dioxide, ammonium phosphate and strontium oxide, stoichiometrically weigh.Secondly the powder that will be weighed
Body material and deionized water are 1 according to mass ratio：Slurry agitation is dried after ball milling mixing is uniform by 50 ball milling mixings.After drying
Powder body be placed in Muffle furnace, in 900 DEG C of roasting temperatures 10 hours, natural cooling obtained Li4Ti5O12/LiTi2P3O12Powder body
Material.By Li4Ti5O12/LiTi2P3O12Powder body, polysorbate40, deionized water are 1 according to mass ratio：0.25：50 weigh ball milling mixing
Stirring and drying after uniform.The last dried powder body of previous step is placed in nitrogen atmosphere protection stove, in 750 DEG C of roasting temperatures
2 hours, natural cooling obtained final Li4Ti5O12/Li4Ti5O12/LiTi2P3O12/ C negative materials.
The lithium titanate battery of the present embodiment, including positive plate, negative plate and barrier film, negative plate by negative current collector aluminium foil and
The Li being coated on negative current collector4Ti5O12/Li4Ti5O12/LiTi2P3O12/ C layers are constituted.Positive plate is by plus plate current-collecting body aluminium foil
Constitute with the positive-material lithium manganate layer being coated on plus plate current-collecting body.Positive plate and negative plate adopt the side of interlaced lamination
Formula is assembled, and the area of negative plate is more than the area of positive plate, so that negative plate can be made to cover positive plate.
Embodiment 6
Li used by the lithium titanate battery of the present embodiment4Ti5O12Negative material, concrete composition are Li4Ti5O12For 96 parts,
Li1+2xM2yTi(2-x-y)P3O12-x(x=0, y=0.2, M=Sc) is 3 parts, 1 part of carbon-coating.Li4Ti5O12Negative material.Preparation process
It is as follows：
First by lithium carbonate, titanium dioxide, ammonium phosphate and strontium oxide, stoichiometrically weigh.Secondly the powder that will be weighed
Body material and deionized water are 1 according to mass ratio：Slurry agitation is dried after ball milling mixing is uniform by 50 ball milling mixings.After drying
Powder body be placed in Muffle furnace, in 1000 DEG C of roasting temperatures 10 hours, natural cooling obtained Li4Ti5O12/
Li1Sr0.4Ti1.8P3O12Powder body material.By Li4Ti5O12/Li1Sr0.4Ti1.8P3O12Powder body, polysorbate40, deionized water are according to quality
Than for 1：0.1：10 weigh the uniform rear stirring and drying of ball milling mixing.The last dried powder body of previous step is placed in nitrogen atmosphere guarantor
In furnace retaining, in 750 DEG C of roasting temperatures 2 hours, natural cooling obtained final Li4Ti5O12/Li1Sr0.4Ti1.8P3O12/ C negative poles
Material.
The lithium titanate battery of the present embodiment, including positive plate, negative plate and barrier film, negative plate by negative current collector aluminium foil and
The Li being coated on negative current collector4Ti5O12/Li1Sr0.4Ti1.8P3O12/ C layers are constituted.Positive plate by plus plate current-collecting body aluminium foil and
The positive-material lithium manganate being coated on plus plate current-collecting body and nickel cobalt aluminic acid lithium layer are constituted.Positive plate and negative plate are using mutually friendship
The mode of wrong lamination is assembled, and the area of negative plate is more than the area of positive plate, so that negative plate can be made to cover positive plate.
According to above-described embodiment, the present invention just can be realized well.
Claims (7)
1. a kind of Li4Ti5O12Negative material, it is characterised in that Li4Ti5O12Negative material structural formula Li4Ti5O12/Li1+ 2xM2yTi(2-x-y)P3O12-x/ C, with multi-layer core-shell structure, by the Li at center4Ti5O12Material and the Li of centre1+2xM2yTi(2-x-y)
P3O12-xLayer and surface conductive carbon layer constitute, wherein x, y be 0～0.2, M be Mg, Sc, Al in one or two,
Li4Ti5O12For 95-98 parts, Li1+2xM2yTi(2-x-y)P3O12-xFor 1-4 parts, carbon-coating 0.1-1 parts；Li4Ti5O12It is prepared by negative material
Comprise the following steps：
A, by the compound of Li source compound, titanium dioxide, P source compound and doped chemical M, stoichiometrically weigh；
B, by the powder body material and liquid in step A according to mass ratio be 1：10～1：50 weigh deionized water, ethanol or acetone
As dispersant；Stirring and drying after ball milling mixing is uniform；
C, dried powder body in step B is placed in Muffle furnace, in 800 DEG C～1200 DEG C roasting temperatures 6～20 hours, from
So cooling obtains required powder body material；
D, the powder body material by step C, carbon source and deionized water are 1 according to mass ratio：0.1：10～1：0.25：50 weigh ball
Stirring and drying after mill mix homogeneously；
E, dried powder body in step D is placed in nitrogen atmosphere protection stove, in 500 DEG C～750 DEG C roasting temperatures 2～6
Hour, natural cooling obtains final Li4Ti5O12Negative material.
2. a kind of Li according to claim 14Ti5O12Negative material, it is characterised in that described Li source compound is selected from
Any one in Lithium hydrate, lithium carbonate, lithium oxalate, lithium acetate, lithium dihydrogen phosphate, lithium nitrate or Quilonorm (SKB).
3. a kind of Li according to claim 14Ti5O12Negative material, it is characterised in that the chemical combination of described doped chemical M
Thing is any one of the oxide, hydroxide or carbonate of Mg, Sc, Al.
4. a kind of Li according to claim 14Ti5O12Negative material, it is characterised in that described P source compound is selected from
In lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium phosphate or ammonium phosphate any one.
5. a kind of Li according to claim 14Ti5O12Negative material, it is characterised in that described carbon source is Tween 80, is told
Temperature 60, any one in polysorbate40.
6. a kind of lithium titanate battery, including positive pole, negative pole, barrier film and electrolyte, it is characterised in that：Described in claim 1
Li4Ti5O12Active substance of the negative material as negative plate.
7. a kind of lithium titanate battery according to claim 6, it is characterised in that the active substance used by positive plate is cobalt acid
One or more in lithium, LiMn2O4, nickle cobalt lithium manganate and nickel cobalt lithium aluminate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109428066A (en) * | 2017-08-30 | 2019-03-05 | 中国科学院宁波材料技术与工程研究所 | Core-shell material and preparation method thereof, lithium ion battery negative material and lithium ion battery |
| CN109920981A (en) * | 2017-12-13 | 2019-06-21 | 广西金茂钛业有限公司 | Lithium battery special-purpose nanometer lithium titanate composite material |
| CN113937260A (en) * | 2021-09-10 | 2022-01-14 | 深圳先进技术研究院 | Lithium titanate/lithium ion conductor/carbon composite material, preparation method and application |
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| CN104779392A (en) * | 2015-04-14 | 2015-07-15 | 淄博蓝印化工有限公司 | Titanium phosphate lithium doped lithium titanate electrode material and manufacturing method thereof |
| CN104916819A (en) * | 2015-05-05 | 2015-09-16 | 天津巴莫科技股份有限公司 | Spinel lithium titanate with low gas production rate and preparation method thereof |
| CN104966822A (en) * | 2015-06-16 | 2015-10-07 | 东莞市翔丰华电池材料有限公司 | Multilayer coated lithium titanate cathode material of lithium ion battery and preparation method of multilayer coated lithium titanate cathode material |
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| CN109428066A (en) * | 2017-08-30 | 2019-03-05 | 中国科学院宁波材料技术与工程研究所 | Core-shell material and preparation method thereof, lithium ion battery negative material and lithium ion battery |
| CN109920981A (en) * | 2017-12-13 | 2019-06-21 | 广西金茂钛业有限公司 | Lithium battery special-purpose nanometer lithium titanate composite material |
| CN113937260A (en) * | 2021-09-10 | 2022-01-14 | 深圳先进技术研究院 | Lithium titanate/lithium ion conductor/carbon composite material, preparation method and application |
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