CN103078087A - Preparation method of lithium titanate/carbon nano tube composite cathode material - Google Patents
Preparation method of lithium titanate/carbon nano tube composite cathode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a lithium titanate/carbon nano tube composite cathode material and belongs to the technical field of battery materials. A carbon nano tube grows on the surface of lithium titanate by a chemical vapour deposition method, and has the characteristics of uniform dispersion, high binding force and the like compared with a carbon nano tube directly doped in lithium titanate, the growing carbon nano tube can form a network structure on the surface of lithium titanate, and an important effect is exerted on improving structural stability of the material under the condition of high-rate discharge of a battery. The contact probability of the lithium ion battery with lithium titanate is increased and the internal resistance and polarization are reduced by using high conductivity of the carbon nano tube and the network structure formed by the carbon nano tube, the liquid absorption and keeping ability of the cathode material can be improved due to larger specific surface area of the carbon nano tube, and the high-rate discharge ability and recyclability of the battery are improved.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, relate to specifically a kind of preparation method of lithium titanate/carbon/carbon nano tube composite negative pole material, belong to the battery material technical field.
Background technology
Lithium ion battery is a kind of novel energy storage cell that grew up in recent years, concern so that it has extended cycle life, working voltage platform is steady, the advantage such as cheap and pollution-free is subject to people now has been widely used in the fields such as electric automobile, wind energy energy storage, mobile power station.
At present, lithium ion battery negative adopts graphite type material more, but the graphite negative electrodes material since cycle life is poor, fail safe is low etc. drawbacks limit its extensive use in field of batteries.Spinel type lithium titanate is a kind of zero strain material, have good cycle, with electrolyte reaction, the charging/discharging voltage platform is steady, safe, price is low and the advantage such as easy preparation, is the desirable negative material of preparation long-life, high security battery.Yet, point product stone type lithium titanate material self electronic conductance and ionic conductance are lower, and capacity attenuation is fast when high current charge-discharge, and high rate performance is relatively poor, affect its application under the high current charge-discharge condition, therefore improve the key that high rate performance becomes the lithium titanate practicalization.
At present, improve Li
4Ti
50
12High rate performance is mainly by two approach: the one, lithium titanate is prepared into the nano barium titanate lithium material; The 2nd, doped conducting metal and material with carbon element.Chinese patent (publication number: CN101630732A) disclose the employing sol-gel process a certain proportion of carbon nano tube dispersion liquid and titanium, lithium compound and doped chemical solution mixed after, heat drying makes the gel precursor, and sintering obtains a kind of carbon nano-tube to coat particle diameter be the preparation method of nano level lithium titanate compound under the inert atmosphere.Same Chinese patent (application number: 201110000627.3) also disclose a kind of in lithium titanate directly doped carbon nanometer pipe prepare anode material, thereby improve the method for battery high rate performance.Yet, the composite negative pole material that said method makes, carbon nano-tube and lithium titanate just simply mix, and wherein carbon nano-tube is all relatively poor in lithium titanate surface distributed uniformity and adhesion, and is very limited to the increase rate of battery high rate performance.
Chinese patent (notification number: CN101969112A) disclose a kind of preparation method of negative material, be 100:(0.1～5 in mass ratio with negative material and catalyst) after the mechanical mixture, add in the thermal reaction apparatus, pass to carbon-source gas, and pass to protective gas as carrying source gas, cooling after being incubated 1～72 hour after being warmed up to 400～900 ℃, the mixture of formation negative material, catalyst and carbon nano-tube; Be 1:(1～100 with mixture and oxidant according to mass ratio again) add in the reactor, add water and stir into pastel; Again pastel is heated to 50～400 ℃ of lower reactions 1～20 hour, makes the composite negative pole material that is coated with carbon nano-tube.Yet the method course of reaction is complicated, the negative material less stable that makes, and the employing oxidation step can destroy the rock-steady structure of lithium titanate self, finally affects the cycle performance of battery.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of lithium titanate/carbon/carbon nano tube composite negative pole material is to improve high rate performance and the cycle performance of battery.
In order to realize above purpose, the technical solution adopted in the present invention is:
A kind of preparation method of lithium titanate/carbon/carbon nano tube composite negative pole material; concrete steps are as follows: be that to add particle diameter in the lithium titanate powder of 0.3～10 μ m be the catalyst fines mixing of 30～100nm at particle diameter; mixed-powder is heated to 600～800 ℃ under atmosphere of hydrogen; be to pass into acetylene gas under 800～1200 ℃ in temperature then; constant temperature is 24～48 hours again; product behind the constant temperature is cooled to room temperature under inert gas shielding, removes catalyst and get final product.
Described catalyst is iron, cobalt, nickel, ferric nitrate, nickel nitrate, iron chloride or nickel chloride.
The weight ratio of described lithium titanate powder and catalyst is lithium titanate powder: catalyst=10:(0.1～1).
Described inert gas is nitrogen, argon gas or helium.
Described lithium titanate powder can be prepared by a conventional method to obtain, and also can be the commercial goods.The present invention only provides a kind of concrete method for preparing lithium titanate powder; step is as follows: be lithium according to mol ratio: titanium: dispersant=1:(1.2 ~ 2): (3～8) get lithium source, titanium source and dispersant; ball milling to particle size is 0.5～5 μ m behind the mixing; dry; under inert gas shielding dried powder being calcined 1～48 hour under 600～1000 ℃, is that 0.3～10 μ m namely gets lithium titanate powder with powder ball milling to the granularity after the calcining.
Described lithium source is lithium carbonate, lithium acetate, lithium nitrate or lithium hydroxide.
Described titanium source is titanium dioxide.
Described dispersant is absolute ethyl alcohol.
Beneficial effect of the present invention:
The present invention adopts chemical vapour deposition technique in lithium titanate superficial growth carbon nano-tube, its with directly in lithium titanate doped carbon nanometer pipe compare and have the characteristic such as be uniformly dispersed, adhesion is strong, the carbon nano-tube of growth is easier simultaneously forms network configuration on the lithium titanate surface, and the Stability Analysis of Structures that improves battery material under large multiplying power discharging condition is played an important role.
Lithium ion battery of the present invention by utilizing carbon nano-tube high conductivity and the network configuration of formation to improve the contact probability with lithium titanate, reduce internal resistance, reduce polarization, the larger specific area of carbon nano-tube can improve again the imbibition liquid-keeping property of negative material simultaneously, thereby improves the large multiplying power discharging ability of battery and the circulation ability of battery.
In a word, the composite negative pole material that adopts chemical vapour deposition technique to prepare in lithium titanate superficial growth carbon nano-tube, can improve conductivity and the large multiplying power discharging ability of lithium titanate, can improve again imbibition ability and the cyclical stability of battery, preferably impetus has been played in the extensive use of lithium titanate negative material; And the preparation method is simple, quick, good stability, and cost is low, is suitable for large-scale production and application.
Description of drawings
Fig. 1 is the Electronic Speculum figure of the embodiment of the invention 1 preparation negative material;
Fig. 2 is the multiplying power discharging figure of lithium ion battery among the embodiment 1;
Fig. 3 is the cyclic curve figure of lithium ion battery in embodiment and the Comparative Examples.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail, but does not consist of any limitation of the invention.
Embodiment 1
The lithium titanate/carbon/carbon nano tube composite negative pole material prepares by following method in the present embodiment, and concrete steps are:
(1) preparation of lithium titanate powder: be lithium according to mol ratio: titanium: dispersant=1:1.2:5 gets lithium carbonate, titanium dioxide and absolute ethyl alcohol, mix in the rear adding planetary ball mill, rotating speed wet ball grinding take 400 rev/mins of speed obtained particle diameter in 48 hours as 2 μ m powder, with powder 100 ℃ of lower freeze-day with constant temperature 2 hours, under argon shield, dried powder was calcined 12 hours under 800 ℃, powder after the calcining is cooled to 100 ℃ of lower taking-ups, adds again that the rotating speed ball milling take 1000 rev/mins namely got particle diameter in 120 minutes as the lithium titanate powder of 1 μ m in the ultra-fine ball mill;
(2) be that to add particle diameter in the lithium titanate powder of 2 μ m be that the iron catalyst mixing of 50nm gets mixed-powder at step (1) particle diameter, the weight ratio of described lithium titanate powder and iron is lithium titanate powder: iron=10:0.5, mixed-powder is added in the quartz tube reactor, and in described reactor, pass into hydrogen, speed with 10 ℃/minute in passing into the process of hydrogen rises to 600 ℃ with the temperature in the reactor, be to pass into acetylene gas under 800 ℃ 100 minutes in temperature then, constant temperature 24 hours, product in the constant temperature post-reactor is cooled to room temperature under nitrogen atmosphere, afterwards through concentrated sulfuric acid washing, distilled water washing, 80 ℃ of dryings after 6 hours ball milling namely get the lithium titanate/carbon/carbon nano tube composite negative pole material.Surface Electronic Speculum figure sees Fig. 1 for details.
The negative material of the present embodiment lithium ion adopts the above-mentioned lithium titanate/carbon/carbon nano tube composite negative pole material for preparing, and positive electrode is the battery LiFePO4, and electrolyte is 1.0mol/L LiPF
6/ EC+DEC(V
EC: V
DEC=1: 1) (EC: ethylene carbonate, DEC: diethyl carbonate), barrier film is U.S. Celgard2300 barrier film, and the performance of the 2.5AH lithium ion battery that makes sees following table 1,2 for details, and multiplying power discharging figure and cyclic curve see Fig. 2, Fig. 3 for details.
Embodiment 2
The lithium titanate/carbon/carbon nano tube composite negative pole material prepares by following method in the present embodiment, and concrete steps are:
(1) preparation of lithium titanate powder: be lithium according to mol ratio: titanium: dispersant=1:2:3 gets lithium nitrate, titanium dioxide and absolute ethyl alcohol, mix in the rear adding planetary ball mill, rotating speed wet ball grinding take 400 rev/mins of speed obtained particle diameter in 48 hours as 5 μ m powder, with powder 100 ℃ of lower freeze-day with constant temperature 3 hours, under nitrogen protection, dried powder was calcined 24 hours under 1000 ℃, powder after the calcining is cooled to 100 ℃ of lower taking-ups, adds again that the rotating speed ball milling take 2000 rev/mins namely got particle diameter in 300 minutes as the lithium titanate powder of 3 μ m in the ultra-fine ball mill;
(2) be that to add particle diameter in the lithium titanate powder of 3 μ m be that the Co catalysts mixing of 100nm gets mixed-powder at step (1) particle diameter, the weight ratio of described lithium titanate powder and cobalt is lithium titanate powder: cobalt=10:1, mixed-powder is added in the quartz tube reactor, and in described reactor, pass into hydrogen, speed with 20 ℃/minute in passing into the process of hydrogen rises to 800 ℃ with the temperature in the reactor, be to pass into acetylene gas under 1000 ℃ 200 minutes in temperature then, constant temperature 24 hours, product in the constant temperature post-reactor is cooled to room temperature under nitrogen atmosphere, afterwards through concentrated sulfuric acid washing, distilled water washing, 80 ℃ of dryings after 6 hours ball milling namely get the lithium titanate/carbon/carbon nano tube composite negative pole material.
The negative material of the present embodiment lithium ion adopts the above-mentioned lithium titanate/carbon/carbon nano tube composite negative pole material for preparing, and positive electrode is the battery LiFePO4, and electrolyte is 1.0mol/L LiPF
6/ EC+DEC(V
EC: V
DEC=1: 1) (EC: ethylene carbonate, DEC: diethyl carbonate), barrier film is U.S. Celgard2300 barrier film, and the performance of the 2.5AH lithium ion battery that makes sees following table 1 for details, and cyclic curve sees Fig. 3 for details.
Embodiment 3
The lithium titanate/carbon/carbon nano tube composite negative pole material prepares by following method in the present embodiment, and concrete steps are:
(1) preparation of lithium titanate powder: be lithium according to mol ratio: titanium: dispersant=1:2:8 gets lithium acetate, titanium dioxide and absolute ethyl alcohol, mix in the rear adding planetary ball mill, rotating speed wet ball grinding take 400 rev/mins of speed obtained particle diameter in 48 hours as 0.5 μ m powder, with powder 100 ℃ of lower freeze-day with constant temperature 4 hours, under the helium protection, dried powder was calcined 48 hours under 600 ℃, powder after the calcining is cooled to 100 ℃ of lower taking-ups, adds again that the rotating speed ball milling take 1500 rev/mins namely got particle diameter in 200 minutes as the lithium titanate powder of 0.3 μ m in the ultra-fine ball mill;
(2) be that to add particle diameter in the lithium titanate powder of 0.3 μ m be that the Raney nickel mixing of 30nm gets mixed-powder at step (1) particle diameter, the weight ratio of described lithium titanate powder and nickel is lithium titanate powder: nickel=10:0.1, mixed-powder is added in the quartz tube reactor, and in described reactor, pass into hydrogen, speed with 20 ℃/minute in passing into the process of hydrogen rises to 600 ℃ with the temperature in the reactor, be to pass into acetylene gas under 900 ℃ 50 minutes in temperature then, constant temperature 48 hours, product in the constant temperature post-reactor is cooled to room temperature under nitrogen atmosphere, afterwards through concentrated sulfuric acid washing, distilled water washing, 60 ℃ of dryings after 8 hours ball milling namely get the lithium titanate/carbon/carbon nano tube composite negative pole material.
The negative material of the present embodiment lithium ion adopts the above-mentioned lithium titanate/carbon/carbon nano tube composite negative pole material for preparing, and positive electrode is the battery LiFePO4, and electrolyte is 1.0mol/L LiPF
6/ EC+DEC(V
EC: V
DEC=1: 1) (EC: ethylene carbonate, DEC: diethyl carbonate), barrier film is U.S. Celgard2300 barrier film, and the performance of the 2.5AH lithium ion battery that makes sees following table 1 for details, and cyclic curve sees Fig. 3 for details.
Embodiment 4
The lithium titanate/carbon/carbon nano tube composite negative pole material prepares by following method in the present embodiment, and concrete steps are:
(1) preparation of lithium titanate powder: be lithium according to mol ratio: titanium: dispersant=1:1.2:8 gets lithium hydroxide, titanium dioxide and absolute ethyl alcohol, mix in the rear adding planetary ball mill, rotating speed wet ball grinding take 400 rev/mins of speed obtained particle diameter in 48 hours as 0.5 μ m powder, with powder 100 ℃ of lower freeze-day with constant temperature 1 hour, under argon shield, dried powder was calcined 30 hours under 700 ℃, powder after the calcining is cooled to 100 ℃ of lower taking-ups, adds again that the rotating speed ball milling take 2000 rev/mins namely got particle diameter in 200 minutes as the lithium titanate powder of 1 μ m in the ultra-fine ball mill;
(2) be that to add particle diameter in the lithium titanate powder of 1 μ m be that the ferric nitrate catalyst mixing of 50nm gets mixed-powder at step (1) particle diameter, the weight ratio of described lithium titanate powder and ferric nitrate is lithium titanate powder: ferric nitrate=10:0.3, mixed-powder is added in the quartz tube reactor, and in described reactor, pass into hydrogen, speed with 10 ℃/minute in passing into the process of hydrogen rises to 1000 ℃ with the temperature in the reactor, be to pass into acetylene gas under 850 ℃ 300 minutes in temperature then, constant temperature 1 hour, product in the constant temperature post-reactor is cooled to room temperature under nitrogen atmosphere, afterwards through concentrated sulfuric acid washing, distilled water washing, 60 ℃ of dryings after 8 hours ball milling namely get the lithium titanate/carbon/carbon nano tube composite negative pole material.
The negative material of the present embodiment lithium ion adopts the above-mentioned lithium titanate/carbon/carbon nano tube composite negative pole material for preparing, and positive electrode is the battery LiFePO4, and electrolyte is 1.0mol/L LiPF
6/ EC+DEC(V
EC: V
DEC=1: 1) (EC: ethylene carbonate, DEC: diethyl carbonate), barrier film is U.S. Celgard2300 barrier film, and the performance of the 2.5AH lithium ion battery that makes sees following table 1 for details, and cyclic curve sees Fig. 3 for details.
Embodiment 5
The lithium titanate/carbon/carbon nano tube composite negative pole material prepares by following method in the present embodiment, and concrete steps are:
(1) preparation of lithium titanate powder: be lithium according to mol ratio: titanium: dispersant=1:1.2:3 gets lithium hydroxide, titanium dioxide and absolute ethyl alcohol, mix in the rear adding planetary ball mill, rotating speed wet ball grinding take 400 rev/mins of speed obtained particle diameter in 48 hours as 5 μ m powder, with powder 100 ℃ of lower freeze-day with constant temperature 4 hours, under argon shield, dried powder was calcined 30 hours under 700 ℃, powder after the calcining is cooled to 100 ℃ of lower taking-ups, adds again that the rotating speed ball milling take 2000 rev/mins namely got particle diameter in 200 minutes as the lithium titanate powder of 10 μ m in the ultra-fine ball mill;
(2) be that to add particle diameter in the lithium titanate powder of 10 μ m be that the nickel chloride iron catalyst mixing of 80nm gets mixed-powder at step (1) particle diameter, the weight ratio of described lithium titanate powder and nickel chloride is lithium titanate powder: nickel chloride=10:0.5, mixed-powder is added in the quartz tube reactor, and in described reactor, pass into hydrogen, speed with 10 ℃/minute in passing into the process of hydrogen rises to 800 ℃ with the temperature in the reactor, be to pass into acetylene gas under 1000 ℃ 60 minutes in temperature then, constant temperature 24 hours, product in the constant temperature post-reactor is cooled to room temperature under nitrogen atmosphere, afterwards through concentrated sulfuric acid washing, distilled water washing, 60 ℃ of dryings after 8 hours ball milling namely get the lithium titanate/carbon/carbon nano tube composite negative pole material.
The negative material of the present embodiment lithium ion adopts the above-mentioned lithium titanate/carbon/carbon nano tube composite negative pole material for preparing, and positive electrode is the battery LiFePO4, and electrolyte is 1.0mol/L LiPF
6/ EC+DEC(V
EC: V
DEC=1: 1) (EC: ethylene carbonate, DEC: diethyl carbonate), barrier film is U.S. Celgard2300 barrier film, and the performance of the 2.5AH lithium ion battery that makes sees following table 1 for details, and cyclic curve sees Fig. 3 for details.
Comparative Examples 1
The positive electrode of this Comparative Examples lithium ion is pure lithium titanate, and electrolyte is 1.0mol/L LiPF
6/ EC+DEC(V
EC: V
DEC=1: 1) (EC: ethylene carbonate, DEC: diethyl carbonate), barrier film is U.S. Celgard2300 barrier film, and the performance of the 2.5AH lithium ion battery that makes sees following table 1 for details, and cyclic curve sees Fig. 3 for details.
Comparative Examples 2
The lithium titanate/carbon/carbon nano tube composite negative pole material prepares by following method in this Comparative Examples, and concrete steps are:
(1) preparation of lithium titanate powder: be lithium according to mol ratio: titanium: dispersant=1:1.2:3 gets lithium hydroxide, titanium dioxide and absolute ethyl alcohol, mix in the rear adding planetary ball mill, rotating speed wet ball grinding take 400 rev/mins of speed obtained particle diameter in 48 hours as 5 μ m powder, with powder 100 ℃ of lower freeze-day with constant temperature 10 hours, under argon shield, dried powder was calcined 30 hours under 700 ℃, powder after the calcining is cooled to 100 ℃ of lower taking-ups, adds again that the rotating speed ball milling take 2000 rev/mins namely got particle diameter in 200 minutes as the lithium titanate powder of 10 μ m in the ultra-fine ball mill;
(2) be that to add particle diameter in the lithium titanate powder of 10 μ m be that the nickel chloride iron catalyst mixing of 80nm gets mixed-powder at step (1) particle diameter, the weight ratio of described lithium titanate powder and nickel chloride is lithium titanate powder: nickel chloride=10:0.5, mixed-powder is added in the quartz tube reactor, and in described reactor, pass into hydrogen, speed with 10 ℃/minute in passing into the process of hydrogen rises to 800 ℃ with the temperature in the reactor, be to pass into acetylene gas under 1000 ℃ 60 minutes in temperature then, constant temperature 24 hours, product in the constant temperature post-reactor is cooled to room temperature under nitrogen atmosphere, again according to quality than product: concentrated hydrochloric acid, add water after the mixed acid of hydrofluoric acid=1:50 mixes and stir into starchiness, programming rate with 5 ℃/min is heated to 300 ℃ of reactions 5 hours, in course of reaction, stirred once every 1 hour, after with the starchiness thing move under the rotating speed of 300r/min, continue in the centrifuge washing equipment to add water washing to the pH of slurry for neutral, centrifugal dehydration makes moisture be lower than 40%, dries to moisture to be lower than 0.01% and get final product under 100 ℃ again.
The negative material of this Comparative Examples lithium ion adopts the above-mentioned lithium titanate/carbon/carbon nano tube composite negative pole material for preparing, and positive electrode is the battery LiFePO4, and electrolyte is 1.0mol/L LiPF
6/ EC+DEC(V
EC: V
DEC=1: 1) (EC: ethylene carbonate, DEC: diethyl carbonate), barrier film is U.S. Celgard2300 barrier film, and the performance of the 2.5AH lithium ion battery that makes sees following table 1 for details, and cyclic curve sees Fig. 3 for details.
The comparison of lithium ion battery high rate performance in table 1 embodiment and the Comparative Examples
The comparison of cycle performance of lithium ion battery in table 2 embodiment and the Comparative Examples
Claims (7)
1. the preparation method of a lithium titanate/carbon/carbon nano tube composite negative pole material; it is characterized in that: concrete steps are as follows: be that to add particle diameter in the lithium titanate powder of 0.3～10 μ m be the catalyst fines mixing of 30～100nm at particle diameter; mixed-powder is heated to 600～800 ℃ under atmosphere of hydrogen; be to pass into acetylene gas under 800～1200 ℃ in temperature then; constant temperature is 24～48 hours again; product behind the constant temperature is cooled to room temperature under inert gas shielding, removes catalyst and get final product.
2. the preparation method of lithium titanate/carbon/carbon nano tube composite negative pole material according to claim 1, it is characterized in that: described catalyst is iron, cobalt, nickel, ferric nitrate, nickel nitrate, iron chloride or nickel chloride.
3. the preparation method of lithium titanate/carbon/carbon nano tube composite negative pole material according to claim 1, it is characterized in that: the weight ratio of described lithium titanate powder and catalyst is lithium titanate powder: catalyst=10:(0.1～1).
4. the preparation method of each described lithium titanate/carbon/carbon nano tube composite negative pole material according to claim 1-3; it is characterized in that: the preparation process of described lithium titanate powder is as follows: be lithium according to mol ratio: titanium: dispersant=1:(1.2 ~ 2): (3～8) get lithium source, titanium source and dispersant; ball milling to particle size is 0.5～5 μ m behind the mixing; dry; under inert gas shielding dried powder being calcined 1～48 hour under 600～1000 ℃, is that 0.3～10 μ m namely gets lithium titanate powder with powder ball milling to the granularity after the calcining.
5. the preparation method of lithium titanate/carbon/carbon nano tube composite negative pole material according to claim 4, it is characterized in that: described lithium source is lithium carbonate, lithium acetate, lithium nitrate or lithium hydroxide.
6. the preparation method of lithium titanate/carbon/carbon nano tube composite negative pole material according to claim 4, it is characterized in that: described titanium source is titanium dioxide.
7. the preparation method of lithium titanate/carbon/carbon nano tube composite negative pole material according to claim 4, it is characterized in that: described dispersant is absolute ethyl alcohol.
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| CN103367716A (en) * | 2013-06-13 | 2013-10-23 | 浙江南博电源科技有限公司 | Preparation method of anode material by growing carbon nano tube on surface of titanium dioxide |
| CN103682296A (en) * | 2013-08-16 | 2014-03-26 | 东莞上海大学纳米技术研究院 | Preparation method for nanoscale lithium titanate material with high specific capacity |
| CN104934589A (en) * | 2015-07-15 | 2015-09-23 | 田东 | Amorphous carbon deposit modified lithium titanate negative electrode material preparation method |
| CN105789620A (en) * | 2014-12-23 | 2016-07-20 | 深圳市比克电池有限公司 | Preparation method of lithium iron phosphate cathode material and lithium iron phosphate cathode material |
| CN106384819A (en) * | 2016-11-07 | 2017-02-08 | 珠海格力电器股份有限公司 | Carbon-coated lithium titanate material and preparation method thereof as well as lithium-ion battery |
| CN107275598A (en) * | 2017-05-27 | 2017-10-20 | 广东烛光新能源科技有限公司 | A kind of lithium titanate anode material and preparation method thereof |
| CN109980223A (en) * | 2017-12-28 | 2019-07-05 | 张家港市国泰华荣化工新材料有限公司 | A kind of lithium titanate/carbon/carbon nano tube composite material and preparation method and application |
| CN110459770A (en) * | 2019-07-31 | 2019-11-15 | 桑顿新能源科技(长沙)有限公司 | A kind of lithium titanate anode material, preparation method, cathode pole piece and lithium ion battery |
| CN110620213A (en) * | 2018-06-20 | 2019-12-27 | 深圳市贝特瑞新能源材料股份有限公司 | Composite material of lithium tetrachloroaluminate and carbon nanotube coated lithium titanate, preparation method and application thereof |
| CN111740104A (en) * | 2020-07-01 | 2020-10-02 | 中南大学 | Preparation method of lithium ferric manganese phosphate/carbon nanotube composite positive electrode material |
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| CN111740104B (en) * | 2020-07-01 | 2021-07-16 | 中南大学 | Preparation method of lithium ferric manganese phosphate/carbon nanotube composite positive electrode material |
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