CN102832382B - Method for preparing nano-lithium titanate cathode material - Google Patents
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- CN102832382B CN102832382B CN201210337220.4A CN201210337220A CN102832382B CN 102832382 B CN102832382 B CN 102832382B CN 201210337220 A CN201210337220 A CN 201210337220A CN 102832382 B CN102832382 B CN 102832382B
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Abstract
The invention discloses a method for preparing a nano cathode material of a lithium ion battery at a low cost. A basic structural formula of the cathode material of the lithium ion battery is Li4Ti5O12 with a cubical spinel structure. The method is characterized by comprising the following steps of (1) sufficiently mixing a lithium salt precursor, TiO2 and a carbon precursor in a water, aqueous solution or solvent environment to obtain a precursor suspension; (2) grinding the precursor suspension; (3) drying the precursor suspension to obtain a precursor mixture; (4) carrying out calcinations on the precursor mixture in an inert atmosphere or inert and air atmosphere; and (5) smashing and grading the clacinated product to obtain a Li4Ti5O12 cathode material or Li4Ti5O12/C composite cathode material. The Li4Ti5O12 cathode material and the Li4Ti5O12/C composite cathode material have excellent electrochemical performance. The invention also provides a nano-electrochemically active cathode material with low cost and uniform particle size distribution produced by the method, and electrodes and batteries manufactured by the nano-electrochemically active cathode material.
Description
Technical field
The present invention relates to a kind of electrochemistry rechargeable battery field, particularly relate to a kind of preparation method of non-anode composite of lithium ion battery and corresponding electrode and battery.
Background technology
Lithium ion battery product from Sony since the commercialization nineties of 20th century, traditional plumbic acid is different from it, NI-G, the charge discharge mechanism of the batteries such as ni-mh and higher volumetric specific energy, gravimetric specific energy and good feature of environmental protection rapid permeability are in each application.The repeated charge principle of lithium ion battery is not limited to the electrochemical reaction between certain specific positive pole and negative material, and its negative or positive electrode material can have multiple choices to match with the needs meeting different application occasion.Most based on graphitic carbon in the lithium ion battery negative material of current acquisition commercial applications.This is mainly because it has relatively high theoretical gram volume and good electron conduction ability and abundant material source.But graphitic carbon also exists following significantly not enough as lithium ion battery negative: (1) is for ensureing the battery charging and discharging long-life, the surface of graphitic carbon negative electrode inevitably consumes Li+ and reacts with electrolyte and generates a kind of solid-electrolyte interface film (SEI) in initial charge and discharge process, this process creates certain irreversible capacity, and SEI film can continue to consume more Li+ with the circulation even destruction that changes, make capacity attenuation, service life reduction; Even more serious situation is, in some carbon graphite negative pole, some product generating SEI film due to reaction is inserted in graphitic carbon side plane structure and impels negative pole structure to cave in cause battery can not normally discharge and recharge and limit some excellent electrolyte solvent as the application of PC etc.(2) graphitic carbon can be had an appointment the change in volume of 10% in the process of discharge and recharge, and this change can cause being separated between active material, and pole piece loses electrical conductivity continuity, final shorter battery life, and fail safe reduces.These obvious problems that graphitic carbon itself exists have had a strong impact on its application in electrical network energy storage and power transport field, and this impels people to find other substituting non-carbon negative material to meet lithium ion battery application in these areas.
Lithium titanate (the Li of cubic spinel structure
4ti
5o
12) due to its excellent structural stability, heat and chemical stability are with abundant titanium resource and asepsis environment-protecting receives extensive concern as non-carbon negative material very attractive in lithium ion battery.Lithium titanate just in time can make up the wretched insufficiency that graphitic carbon exists as negative pole because of the uniqueness of its material self: (1) is from the Li of full electric discharge state
4ti
5o
12to the Li of fully charged state
4ti
5o
12in whole charge and discharge process, material is all the time in stable spinel structure, and only there is very little change in volume (being less than 0.2%), therefore be referred to as " zero strain " material, the cycle life that this feature substantially increases respective battery reaches and at least exceedes up to ten thousand times, also improves the fail safe of battery simultaneously; (2) because its voltage platform is at 1.55V vs Li/Li
+, therefore lithium titanate does not react with electrolyte and generates SEI film, can avoid the battery cycle life caused because of the instability of SEI film itself, and fail safe reduces, and has low irreversible capacity simultaneously, even can widen the range of choice of electrolyte solvent.In addition, lithium titanate also has the serviceability temperature scope wider relative to graphitic carbon and better high rate performance.Although its energy density is lower than other lithium ion battery material, but higher than plumbic acid, NI-G etc., have ensured the cycle life of battery security and overlength simultaneously, cause battery manufacture cost greatly to reduce.Therefore this makes to be that the lithium ion battery of negative pole is particluarly suitable for requiring the long-life in electrical network energy storage and means of transportation and electric tool with lithium titanate, the application in fail safe and high power charging-discharging occasion.
The synthetic method of usual lithium titanate has two large classes: one is high-temperature solid phase reaction method; most of known synthetic method appears in following representational document and patent: Tsutomu Ohzuku et al, J.Electrochem.Soc.1995, Vol.142; No.5,1431-1435; Power technology, 2008.2Vol.32No.2,99-101,119; CN102050483A; US6890510B2, US2003/0017104A1, US6706445B2).Take titaniferous at these great majority of the prior art, the compounds precursors of lithium generates active lithium titanate anode material through high temperature solid state reaction, the method technique is simple, flow process is short, production efficiency is high, but the shortcoming of solid phase method is also apparent, owing to being high temperature solid state reaction, there is too much reacting phase and make each mixing being difficult to realize molecular level mutually between middle reactant, therefore the wide and micro-size particles of lack of homogeneity of particle size distribution range can usually be obtained, due to the electronic conductance of Li4Ti5O12 and ionic conductance lower, when high current charge-discharge, capacity attenuation is fast, high rate performance is poor, therefore finally cause the chemical property of material and battery poor.Though make final product cut size reach nano-scale even if this method technique is improved through high-energy mechanical ball milling, but heterogeneous reaction still makes final material electrochemical performance not have the difference (K.Zaghib of essence with the micro-size particles without mechanical ball milling, etal., J.Power Sources 81 – 82 (1999) 300).Another kind of synthetic method is sol-gal process (US7368097B2, EP1282180A1, EP1412993A1, Y.H.Rho, et al., J.Electrochem.Soc.151 (2004) A106.), the soluble compound presoma of titaniferous and lithium is characterized in dissolve the reaction that homogeneous phase occurs in a solvent, the mixing that therefore can reach molecular level level obtains the good product of homogeneity, but its process relates to use organometallic reaction thing presoma and organic solvent makes the cost of raw material greatly increase, add manufacturing process complexity, therefore be difficult to realize large-scale industrial production.Therefore a kind of low cost of necessary exploitation, the lithium titanate anode material large-scale method for producing that all even consistency of product cut size is good.
Summary of the invention
For improving the performance of rechargeable battery and reducing synthesis and manufacturing cost, use different processing methods to synthesize lithium titanate anode material.Current industrial main production method is solid phase synthesis process.But just as previously mentioned, the material particle size scope that the method is produced is very large, cause its chemical property especially rate charge-discharge and cycle life poor.This is because the performance of battery electrode material depends on the form of material, granularity, purity and conductance to a great extent.Different materials synthesis technique can be used and produce the material with different shape, granularity, purity or conductance.Therefore the performance height of battery material depends on synthesis technique.For improving the electronic conductivity of material and needing to carry out grain diameter nano, and traditional solid phase synthesis process obtains usually is micron-sized particle, and result causes the quality and performance of synthetic material to affect adversely.
It is seriously constrained in Li-Ion rechargeable battery application commercially for the production of problems such as material homogeneity/cycle life/high costs existing in the conventional method of lithium titanate anode material.The cost existed for the current production lithium titanate of negative pole material of above-mentioned proposition and product homogeneity problem, the invention discloses the method for producing high-quality and high performance nano-lithium titanate cathode material for large-scale manufacture.
The object of this invention is to provide a kind of low cost, nano-lithium titanate cathode material production technology that product cut size is evenly distributed.Technical thought of the present invention is intended to by reducing the reaction number of phases and being coated with last layer carbonaceous conductive layer to suppress crystal to be grown up and the nanoscale degree of depth selecting removing carbonaceous conductive layer to reach between reactant with the technical method improving material specific capacity in follow-up process treatment process mixes and generates stable nanosized product at the process situ generating active cathode material.The negative pole lithium titanate material that method is produced thus can overcome the drawback in traditional high temperature solid-state method and sol-gal process simultaneously, material is because particle diameter is in nano-scale and narrowly distributing and have excellent chemical property, the inexpensive asepsis environment-protecting of abundant raw materials simultaneously, technical process is simple and cost is low, production and processing time consumption and energy consumption is low, react controlled, therefore the technology of the present invention advance and to realize the advantage of industrialization apparent.
In order to solve these problems in currently available technology, technical scheme provided by the invention is:
By abundance and the method for lithium ion battery non-carbon negative material produced by inexpensive raw material, described negative material is Li
4ti
5o
12or Li
4ti
5o
12/ C composite, wherein Li
4ti
5o
12in cubic spinel structure.It is characterized in that said method comprising the steps of:
(1) at water, under the aqueous solution or solvent existent condition, fully lithium salts presoma is mixed, TiO
2and carbon matrix precursor obtains presoma suspension-turbid liquid;
(2) presoma suspension-turbid liquid is ground;
(3) dry presoma suspension-turbid liquid obtains precursor mixture at a certain temperature;
(4) in inert atmosphere or inert atmosphere+air, precursor mixture is calcined;
(5) calcined product pulverized and classifiedly obtain final products spinelle Li
4ti
5o
12negative material or Li
4ti
5o
12/ C composite negative pole material.
Preferably, in described method, lithium salts presoma is selected from Li
2cO
3, Li
2c2O
4, LiOH, LiCH
3one or more combination in any in COO.
Preferably, in described method, carbon matrix precursor is selected from one or more combination in any of polyoxyethylene (PEO), polyvinyl alcohol (PVA), monose, polysaccharide, polyethers, polyethylene glycol, polyester, PCL, polyactide, poly butylene succinate, poly-succinic adipic acid, poly terephthalic acid succinic acid-butanediol ester, poly-hydracrylic acid, poly butyric ester, poly-hydroxypentanoic acid, poly-hydroxycaproic ester, poly-3-Hydroxyoctanoic acid ester, poly-3-hydroxy phenyl valeric acid and poly-3-hydroxy phenyl caproic acid.
Preferably, in described method, solvent is selected from isopropyl alcohol, acetone or deionized water.
Preferably, TiO in described method
2structure is selected to be one or both mixtures in sharp titanium stone-type or rutile-type.
Preferably, in described method, the use amount of lithium salts and titanium precursors is that the ratio being 0.7 ~ 0.9 with lithium and titanium mol ratio is prepared burden.
Preferably, in described method, the use amount of carbon matrix precursor accounts between lithium and 2% ~ 20% of titanium precursors total weight.
Preferably, in described method, baking temperature controls between 100 DEG C ~ 220 DEG C.
Preferably, the temperature of calcining precursor mixture in described method controls between 400 DEG C ~ 1200 DEG C, and calcination time is 1 ~ 6 hour.
Preferably, calcining precursor mixture in described method can carry out all the time in an inert atmosphere, also can be the first short time in an inert atmosphere, then carry out in atmosphere.
Preferably, calcined product is also comprised in described procedure through pulverizing and classification process.
Another object of the present invention is to provide a kind of negative material for electrochemical cell, and its formation process comprises the following steps:
(1) lithium salts presoma is mixed, TiO
2and soluble carbon presoma obtains presoma suspension-turbid liquid;
(2) presoma suspension-turbid liquid is ground;
(3) dry presoma suspension-turbid liquid obtains precursor mixture;
(4) precursor mixture is calcined;
(5) pulverize and finally obtain Li after classified calcined product
4ti
5o
12negative material or Li
4ti
5o
12/ C composite negative pole material.
In one embodiment of the invention, calcining precursor mixture carries out all the time in an inert atmosphere, finally obtains Li
4ti
5o
12/ C composite negative pole material.
In another embodiment of the invention, calcining precursor mixture be the first short time in an inert atmosphere, then carry out in atmosphere, finally obtain Li
4ti
5o
12negative material.
Another object of the present invention is to provide a kind of electrochemical cell, comprising:
(1) anode, its Anodic is a kind of by anode according to claim 8.
(2) electrolyte;
(3) negative electrode;
(4) barrier film.
Relative to scheme of the prior art, advantage of the present invention is: the invention provides a kind of low cost, nano-lithium titanate cathode material production technology that product cut size is evenly distributed.By reducing the reaction number of phases and original position is coated with last layer carbonaceous conductive layer to suppress crystal to be grown up and select removing carbonaceous conductive layer to mix with the technical method the improving material specific capacity nanoscale reached between reactant in follow-up process treatment process and guarantee that the negative material of generation is stabilized in nano-scale in the active cathode material generated.The negative pole lithium titanate material that method is produced thus can overcome exist in traditional high temperature solid-state method and sol-gal process as large in particle size simultaneously and distribute wide; complex technical process; the a series of drawbacks such as calcining heat and time length; the not only inexpensive asepsis environment-protecting of abundant raw materials; technical process is simple; react controlled; production and processing time consumption and energy consumption is low; and product is because particle diameter is in nano-scale and narrowly distributing and evenly; therefore there is excellent chemical property, the advantage as can be seen here on the advance of the technology of the present invention and industrial scale.In sum, the invention provides a kind of integrated cost low, function admirable and be easy to the method for the production lithium titanate anode material realizing industrialization and corresponding electrode and battery.
Accompanying drawing explanation
Below in conjunction with accompanying drawing table and embodiment, the present invention is described in further detail.
Fig. 1 shows the synthesis technique schematic diagram of material in pusher furnace of the embodiment of the present invention 2, and wherein first promoted mainly plate is transported to A stove N to precursor mixture
2short time calcining in atmosphere, is then pushed back plate and to be transported in B stove logical outside air and to calcine.
Fig. 2 shows embodiment 1 synthetic material and conventional solid-state method synthetic material respectively at 5C(A) and 10C (B) condition under when testing sample embodiment 1 contrast relative to the high rate capability of solid phase reaction method, observe the capacity of material under same multiplying power that the capacity under the high magnification be obtained by reacting by conventional solid synthesizes in embodiment 1.
Fig. 3 shows embodiment 1 and the charging and discharging curve of embodiment 2 under different multiplying, can observe under the condition of charge-discharge magnification up to 10C, the charging/discharging voltage of the material synthesized by the embodiment of the present invention 1 is very close, shows that material still has good discharge and recharge invertibity and very low irreversible capacity under high magnification.
Fig. 4 is the capacity of embodiment 1 synthetic material lithium titanate 2032 half-cell and the graph of a relation of cycle-index, wherein show the circulation of electrochemical cell when 5C charge-discharge magnification using this synthetic material as anode material, after 850 weeks charge and discharge cycles, material still has the capacity up to 98.4% to keep.
Table 1 is the electrochemical property test result of lithium titanate 2032 half-cell under different multiplying of synthesis in embodiment 1 and embodiment 2.
Embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiments are not limited to for illustration of the present invention limit the scope of the invention.The implementation condition adopted in embodiment can do further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
Introduce and general introduction
The present invention by way of example but not the mode providing restriction be described.It should be noted, " one " or " one " execution mode described in disclosure file may not refer to same embodiment, and refers to have one at least.
Hereafter various aspects of the present invention will be described.But, those of skill in the art be it is evident that, the present invention can be implemented in only some or all of aspect according to the present invention.For purposes of illustration, provide concrete numbering, material and configuration herein, thoroughly understand the present invention to enable people.But it is evident that for those of skill in the art, the present invention can implement without the need to concrete details.In other examples, for not making the present invention obscure and omitting or simplify well-known feature.
Various operation is described successively as multiple discrete step, and to contribute to most understanding mode of the present invention to illustrate; But, in-order description should be interpreted as that these operations of hint must depend on order.
By according to the reactant of type species, various execution mode is described.It is evident that for those of skill in the art, the present invention can use different types of reactant of any amount to implement, and is not those reactants provided for the purpose of illustration and here.In addition, also it is evident that, the present invention is not limited to any specific mixing example.
Embodiment 1Li
4ti
5o
12the synthesis of/C composite anode active material
In a kind of embodiment of the present invention, Li
4ti
5o
12/ C composite is synthesized by following process:
(1) 1288g Li is weighed
2cO
3, 3480gTiO
2and 286gPVA, load weighted raw material is mixed, PVA is uniformly dispersed in the feed.Proceed in high-energy mills, add after 35L water grinds 3 hours and obtain presoma suspension-turbid liquid.
(2) under 110 DEG C of conditions, drying obtains presoma.
(3) calcine under condition presoma being incubated 2 hours 15 minutes in N2 in calciner at 800 DEG C, product is through pulverizing and obtain after classification process the Li of black gray expandable
4ti
5o
12/ C composite.
Embodiment 2Li
4ti
5o
12the synthesis of negative active core-shell material
In a kind of embodiment of the present invention, Li
4ti
5o
12material is synthesized by following process:
(1) 1288g Li is weighed
2cO
3, 3480gTiO
2and 286gPVA, load weighted raw material is mixed, PVA is uniformly dispersed in the feed.Proceed in high-energy mills, add after 35L water grinds 3 hours and obtain presoma suspension-turbid liquid.
(2) under 110 DEG C of conditions, drying obtains presoma.
(3) by presoma in push-plate type calciner at 800 DEG C N
2calcine under the middle insulation condition of 15 minutes, calcine under the condition being then incubated 2 hours in air at 800 DEG C.Product is through pulverizing and obtain after classification process the Li of white
4ti
5o
12negative material.
Fig. 1 shows the synthesis technique schematic diagram of material in push-plate type calciner of the embodiment of the present invention 2, and wherein first promoted mainly plate is transported to A stove N to precursor mixture
2carry out calcining in 15 minutes in atmosphere, then pushed back plate and to be transported in B stove logical outside air and to carry out calcining in 2 hours.
Li
4ti
5o
12or Li
4ti
5o
12the chemical property of/C composite anode materials is realized by commodity in use button cell.First anode material is prepared on the Copper Foil with PVDF and super P carbon.Lithium metal is used as negative electrode, and 1.3M LiPF
6(in EC/DMC, 1:1(volume ratio)) as electrolyte.
Fig. 2 shows embodiment 1 synthetic material and conventional solid-state method synthetic material respectively at 5C(A) and 10C (B) condition under when testing sample embodiment 1 contrast relative to the high rate capability of solid phase reaction method, observe the capacity of material under same multiplying power that the capacity under the high magnification be obtained by reacting by conventional solid synthesizes in embodiment 1.
Fig. 3 shows embodiment 1 and the charging and discharging curve of embodiment 2 under different multiplying, can observe under the condition of charge-discharge magnification up to 10C, the charging/discharging voltage of the material synthesized by the embodiment of the present invention 1 is very close, shows that material still has good discharge and recharge invertibity and very low irreversible capacity under high magnification.
Table 1 is the electrochemical property test result of lithium titanate 2032 half-cell under different multiplying of synthesis in embodiment 1 and embodiment 2, can find out embodiment 1 with 2-in-1 become material electrochemical performance very close, it should be noted that, embodiment 2 consumes less inert atmosphere compared with embodiment 1, therefore on process costs, has more advantage.
Fig. 4 is the capacity of embodiment 1 synthetic material lithium titanate 2032 half-cell and the graph of a relation of cycle-index, wherein show the circulation of electrochemical cell when 5C charge-discharge magnification using this synthetic material as anode material, after 850 weeks charge and discharge cycles, material still has the capacity up to 98.4% to keep.
The electrochemical property test result of table 1 lithium titanate 2032 half-cell under different multiplying
The Li prepared by the present invention as can be seen here
4ti
5o
12and Li
4ti
5o
12/ C negative material has excellent chemical property relative to the lithium titanate material that conventional solid-state method synthesizes, especially particularly outstanding on high magnification and cycle performance.
In sum, the invention provides the nano-lithium titanate cathode material production technology that a kind of low cost and product cut size are evenly distributed.By reducing the reaction number of phases and original position is coated with last layer carbonaceous conductive layer to suppress crystal to be grown up and to select removing carbonaceous conductive layer to mix with the technical method the improving material specific capacity nanoscale reached between reactant in follow-up process treatment process and the negative material of generation remains on nano-scale in the active cathode material generated.The negative pole lithium titanate material that method is produced thus can overcome the cost and material particle size and homogeneity drawback that exist in traditional high temperature solid-state method and sol-gal process simultaneously, not only abundant raw materials is inexpensive, technical process is simple, react controlled, production and processing time consumption and energy consumption is low, and product is because particle size range is at nanoscale and narrowly distributing and evenly, therefore have excellent chemical property.Therefore the invention provides a kind of integrated cost low, function admirable and be easy to the method for the production lithium titanate anode material realizing industrialization and electrode and battery, this technology is conducive to widening lithium ion battery and is requiring the electrical network energy storage of overlength cycle life and security requirement is high and the application prospect of the power transport field of fast charging and discharging.
The above specific embodiment is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvement or replacement, these improve or replace and also should be considered as protection scope of the present invention.
Claims (7)
1. produce a method for Nanometer Anode Materials for Lithium Ion Batteries, described Nanometer Anode Materials for Lithium Ion Batteries is Li
4ti
5o
12negative material, is characterized in that said method comprising the steps of:
(1) under deionized water existent condition, fully lithium salts presoma, TiO is mixed
2and carbon matrix precursor obtains presoma suspension-turbid liquid;
(2) presoma suspension-turbid liquid is ground;
(3) dry presoma suspension-turbid liquid obtains precursor mixture;
(4) first in an inert atmosphere, then precursor mixture is calcined in atmosphere; The temperature of calcining precursor mixture controls between 400 DEG C ~ 1200 DEG C, and calcination time is 1 ~ 6 hour;
(5) calcined product pulverized and classifiedly finally obtain Nanometer Anode Materials for Lithium Ion Batteries.
2. method according to claim 1, is characterized in that described lithium salts presoma is selected from Li
2cO
3, Li
2c
2o
4, LiOH, LiCH
3one or more combination in any in COO.
3. method according to claim 1, is characterized in that described carbon matrix precursor is selected from one or more combination in any of polyoxyethylene (PEO), polyvinyl alcohol (PVA), monose, polysaccharide, polyethers, polyethylene glycol, polyester, PCL, polyactide, poly butylene succinate, poly-succinic adipic acid, poly terephthalic acid succinic acid-butanediol ester, poly-hydracrylic acid, poly butyric ester, poly-hydroxypentanoic acid, poly-hydroxycaproic ester, poly-3-Hydroxyoctanoic acid ester, poly-3-hydroxy phenyl valeric acid and poly-3-hydroxy phenyl caproic acid.
4. method according to claim 1, is characterized in that described TiO
2structure is selected to be one or both mixtures in sharp titanium stone-type or rutile-type.
5. method according to claim 1, is characterized in that in described method, baking temperature controls between 100 DEG C ~ 220 DEG C.
6. the Li for electrochemical cell
4ti
5o
12negative material, it is prepared from by the method described in any one of claim 1-5.
7. an electrochemical cell, comprising:
(1) anode, its Anodic adopts by the Li for electrochemical cell according to claim 6
4ti
5o
12negative material;
(2) electrolyte;
(3) negative electrode;
(4) barrier film.
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| CN102997651B (en) * | 2012-11-30 | 2015-09-16 | 龙能科技（苏州）有限公司 | Prepare pusher furnace and the method thereof of lithium titanate anode material for lithium ion battery |
| CN103682299A (en) * | 2013-11-27 | 2014-03-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Doped modified lithium titanate composite material and preparation method |
| CN104916846A (en) * | 2015-07-03 | 2015-09-16 | 中国第一汽车股份有限公司 | Preparation method of nano-micron morphology Zn-doped lithium titanate for lithium-ion battery |
| CN108408764A (en) * | 2018-03-09 | 2018-08-17 | 无锡晶石新型能源股份有限公司 | A kind of production technology of nano-scale fiber shape lithium titanate |
| CN109244415A (en) * | 2018-09-29 | 2019-01-18 | 北京泰丰先行新能源科技有限公司 | A kind of preparation method of spherical shape carbon coating titanate composite negative pole material |
| CN111732122A (en) * | 2020-07-03 | 2020-10-02 | 合肥工业大学 | A lithium ion battery based on MIL-125 (Ti) lithium titanate negative electrode material and preparation method thereof |
| CN113707871B (en) * | 2021-09-02 | 2022-08-19 | 和也健康科技有限公司 | Preparation of nanobelt lithium titanate @ stone needle composite fiber material, product and application |
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| CN101428851A (en) * | 2008-12-04 | 2009-05-13 | 上海大学 | Process for producing lithium ion battery negative pole material of lithium titanate |
| CN102376937A (en) * | 2010-08-18 | 2012-03-14 | 中国科学院金属研究所 | Nanometer lithium titanate/graphene composite negative electrode material and preparation process thereof |
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