CN102832382A - Method for preparing nano-lithium titanate cathode material - Google Patents
Method for preparing nano-lithium titanate cathode material Download PDFInfo
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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 and corresponding electrode and battery of non-carbon anode material of lithium ion battery.
Background technology
The lithium ion battery product from Sony since the commercialization nineties of 20th century; Be different from traditional plumbic acid with it; NI-G, the charge discharge mechanism of batteries such as ni-mh and higher volumetric specific energy, gravimetric specific energy and favorable environment protection rapid permeability are in each application.The repeated charge principle of lithium ion battery is not limited to certain specific positive pole and the electrochemical reaction between the negative material, and its negative or positive electrode material can have the multiple choices pairing to satisfy the needs of different application occasion.Most in the lithium ion battery negative material of acquisition commercial applications at present is main with graphitic carbon.This mainly is because it has relative high theoretical gram volume and good electron conductive capability and abundant material source.It is following significantly not enough that yet graphitic carbon exists as lithium ion battery negative: (1) is for guaranteeing the battery charging and discharging long-life; The surface of graphitic carbon negative pole consumes Li+ inevitably and generates a kind of solid-electrolyte interface film (SEI) with the electrolyte reaction in initial charge and discharge process; This process has produced certain irreversible capacity; And the SEI film changes with circulation even destruction can continue to consume more Li+, makes capacity attenuation, and the life-span reduces; Even more serious situation is; In some carbon graphite negative pole, some product that generates the SEI film owing to reaction is inserted into and impels negative pole structure to cave in the graphitic carbon side plane structure to cause battery normally not discharge and recharge the application that has limited some good electrolyte solvent such as PC etc.(2) graphitic carbon 10% the change in volume of in charging and discharging process, can having an appointment, this variation can cause separating between the active material, and pole piece loses the electrical conductivity continuity, final shorter battery life, 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 seek other substituting non-carbon negative pole materials to satisfy lithium ion battery in these Application for Field.
Lithium titanate (the Li of cubic spinel structure
4Ti
5O
12) because its good structural stability, heat and chemical stability have received extensive concern with abundant titanium resource and asepsis environment-protecting as very attractive non-carbon negative pole material in the lithium ion battery.Lithium titanate just in time can remedy 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 discharge attitude
4Ti
5O
12Li to fully charged state
4Ti
5O
12Material is stable spinel structure all the time in the whole charging and discharging process; And very little change in volume (being less than 0.2%) only takes place; So b referred to as " zero strain " material; The cycle life that these characteristics have improved respective battery greatly reaches inferior above up to ten thousand at least, the fail safe that has also improved battery simultaneously; (2) since its voltage platform at 1.55V vs Li/Li
+, so lithium titanate do not generate the SEI film with electrolyte reaction, the battery cycle life that can avoid the instability because of SEI film itself to cause, and the fail safe reduction 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 and better high rate performance wideer with respect to graphitic carbon.Although its energy density is lower than other lithium ion battery material, but be higher than plumbic acid, NI-G etc. have ensured the cycle life of battery security and overlength to cause the battery manufacturing cost to reduce greatly simultaneously.Therefore this makes with the lithium titanate 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 the electric tool application in fail safe and the high power charging-discharging occasion.
Usually the synthetic method of lithium titanate has two big types: the one, and high-temperature solid phase reaction method; Most of known synthetic methods appear in following representational document and the 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 compound presoma of lithium generates active lithium titanate anode material through high temperature solid state reaction; This method technology is simple, flow process is short, production efficiency is high; But the shortcoming of solid phase method also is conspicuous, owing to be high temperature solid state reaction, has too much reacting phase and the very difficult mixing that realizes molecular level between feasible each middle mutually reactant; Therefore can obtain the micro-size particles of the wide and lack of homogeneity of particle size distribution range usually; Because electronic conductance and the ionic conductance of Li4Ti5O12 are lower, capacity attenuation is fast when high current charge-discharge, high rate performance is relatively poor, therefore finally causes the chemical property of material and battery poor.Though make final product cut size can reach nano-scale even this method technology is improved through the high energy mechanical ball milling; But heterogeneous reaction still makes final material electrochemical performance and the micro-size particles without mechanical ball milling not have the difference (K.Zaghib of essence; Et al., 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.), be characterized in the soluble compound presoma of titaniferous and lithium is dissolved in the reaction that homogeneous phase takes place in the solvent; Therefore can reach the mixed good product of homogeneity that gets of molecular level level; Use organometallic reaction thing presoma and organic solvent to make the cost of raw material increase greatly yet its process relates to, add the manufacturing process complicacy, therefore be difficult to realize large-scale industrial production.So a kind of low cost of necessary exploitation, product cut size is the lithium titanate anode material large-scale method for producing of even high conformity all.
Summary of the invention
Synthesize and manufacturing cost with reducing for the performance of improving rechargeable battery, used different processing methods to synthesize lithium titanate anode material.It is solid phase synthesis process that main production methods is gone up in industry at present.Yet as preceding said, the material particle size scope that this method is produced is very big, and especially rate charge-discharge and cycle life are poor to cause its chemical property.This is because the performance of battery electrode material depends on form, granularity, purity and the conductance of material to a great extent.Can use the material different synthesis technique and produce have different shape, the material of granularity, purity or conductance.Therefore the performance height of battery material depends on synthesis technique.For the electronic conductivity that improves material need carry out grain diameter nanoization, be micron-sized particle and traditional solid phase synthesis process obtains usually, the result causes the quality of synthetic material and performance to affect adversely.
Be used for producing problems such as the existing material homogeneity/cycle life of conventional method of lithium titanate anode material/expensive and seriously restricted it in the application of Li-Ion rechargeable battery on market.Cost and product homogeneity problem to the present production negative material lithium titanate of above-mentioned proposition exists the invention discloses the method that is used for changing on a large scale manufacturing production high-quality and high performance nanoscale metatitanic acid cathode of lithium material.
The purpose of this invention is to provide cheaply a kind of, nanoscale metatitanic acid cathode of lithium manufacture of materials that product cut size is evenly distributed technology.Technical thought of the present invention be intended to through reduce the reaction number of phases and in the process that generates active cathode material original position coat one deck carbonaceous conductive layer and reach the nanoscale degree of depth between the reactant with the technical method that improves material specific capacity and mix and generate stabilized nano level product to suppress that crystal is grown up and in follow-up process treatment process, to select to remove the carbonaceous conductive layer.The negative pole lithium titanate material of method production can overcome traditional high temperature solid-state method and the drawback in the sol-gal process simultaneously thus; Material has excellent chemical property because of particle diameter in nano-scale and narrowly distributing; Abundant raw materials cheap and non-toxic environmental protection simultaneously, technical process is simple and cost is low, and the production and processing time consumption and energy consumption is low; React controlled, so the advantage advanced and the realization industrialization of the present invention's technology is obvious.
In order to solve these problems of the prior art at present, technical scheme provided by the invention is:
The method that the abundant and inexpensive raw material in a kind of origin source are produced the non-carbon negative pole material of lithium ion battery, said negative material is Li
4Ti
5O
12Or Li
4Ti
5O
12/ C composite material, wherein Li
4Ti
5O
12Be the cubic spinel structure.It is characterized in that said method comprising the steps of:
(1), fully mixes lithium salts presoma, TiO under the condition that the aqueous solution or solvent exist at water
2And carbon matrix precursor obtains the presoma suspension-turbid liquid;
(2) grind the presoma suspension-turbid liquid;
(3) dry at a certain temperature presoma suspension-turbid liquid obtains precursor mixture;
(4) in inert atmosphere or inert atmosphere+air, calcine precursor mixture;
(5) calcined product is pulverized and the classified final products spinelle Li that obtains
4Ti
5O
12Negative material or Li
4Ti
5O
12/ C composite negative pole material.
Preferably, the lithium salts presoma is selected from Li in the described method
2CO
3, Li
2C2O
4, LiOH, LiCH
3The combination in any of one or more among the COO.
Preferably, carbon matrix precursor is selected from 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, gathers hydracrylic acid, poly butyric ester, gathers hydroxypentanoic acid, gathers hydroxycaproic ester, gathers-3-Hydroxyoctanoic acid ester, gathers-one or more combination in any of 3-hydroxy phenyl valeric acid and gathering-3-hydroxy phenyl caproic acid in the described method.
Preferably, solvent is selected from isopropyl alcohol in the described method, acetone or deionized water.
Preferably, TiO in the described method
2Selecting structure for use is one or both mixtures in sharp titanium stone type or the rutile-type.
Preferably, the use amount of lithium salts and titanium precursor body is to be 0.7 ~ 0.9 ratio batching with lithium and titanium mol ratio in the said method.
Preferably, in the said method use amount of carbon matrix precursor account for lithium and titanium precursor body total weight 2% ~ 20% between.
Preferably, baking temperature is controlled between 100 ℃ ~ 220 ℃ in the said method.
Preferably, the temperature of calcining precursor mixture is controlled between 400 ℃ ~ 1200 ℃ in the said method, and calcination time is 1 ~ 6 hour.
Preferably, in the said method calcining precursor mixture can in inert atmosphere, carry out all the time, also can be the elder generation short time in inert atmosphere, in air, carry out then.
Preferably, comprise also in the said procedure that calcined product is through pulverizing and hierarchical processing.
Another object of the present invention provides a kind of negative material that is used for electrochemical cell, and it forms technology and may further comprise the steps:
(1) mixes lithium salts presoma, TiO
2And the soluble carbon presoma obtains the presoma suspension-turbid liquid;
(2) grind the presoma suspension-turbid liquid;
(3) dry presoma suspension-turbid liquid obtains precursor mixture;
(4) calcining precursor mixture;
(5) finally obtain Li behind pulverizing and the classified calcined product
4Ti
5O
12Negative material or Li
4Ti
5O
12/ C composite negative pole material.
In one embodiment of the invention, the calcining precursor mixture carries out in inert atmosphere all the time, finally obtains Li
4Ti
5O
12/ C composite negative pole material.
In another embodiment of the invention, the calcining precursor mixture be the elder generation short time in inert atmosphere, in air, carry out then, finally obtain Li
4Ti
5O
12Negative material.
Another purpose of the present invention provides a kind of electrochemical cell, comprising:
(1) anode, wherein anode is a kind of by the described anode of claim 8.
(2) electrolyte;
(3) negative electrode;
(4) barrier film.
With respect to scheme of the prior art, advantage of the present invention is: the invention provides cheaply a kind of, nanoscale metatitanic acid cathode of lithium manufacture of materials that product cut size is evenly distributed technology.Through reduce the reaction number of phases and on the active cathode material that generates original position be coated with last layer carbonaceous conductive layer and reached nanoscale between the reactant with the technical method that improves material specific capacity and mix and guarantee that the negative material that generates is stabilized in nano-scale to suppress that crystal is grown up and in follow-up process treatment process, to select to remove the carbonaceous conductive layer.Thus the negative pole lithium titanate material produced of method can overcome simultaneously exist in traditional high temperature solid-state method and the sol-gal process like the product particle diameter greatly and distribute wide; Complex technical process, a series of drawbacks such as calcining heat and time length, not only abundant raw materials cheap and non-toxic environmental protection; Technical process is simple; React controlled, the production and processing time consumption and energy consumption is low, and product is even in nano-scale and narrowly distributing because of particle diameter; Therefore have excellent chemical property, this shows the advance of the present invention's technology and the advantage on the industrial scale.In sum, it is low to the invention provides a kind of integrated cost, and function admirable and being easy to realizes method and the corresponding electrode and the battery of the production lithium titanate anode material of industrialization.
Description of drawings
Below in conjunction with accompanying drawing table and embodiment the present invention is described in further detail.
Fig. 1 shows the synthesis technique sketch map of material in pusher furnace of the embodiment of the invention 2, and wherein precursor mixture is promoted mainly plate earlier and is transported to A stove N
2Short time calcining in the atmosphere is pushed back plate then and is transported to logical outside air calcining in the B stove.
Fig. 2 shows embodiment 1 synthetic material and conventional solid-state method synthetic material, and embodiment 1 is with respect to the high rate capability contrast of solid phase reaction method during specimen under 5C (A) and 10C (B) condition respectively, and the capacity high magnification that is obtained by traditional solid phase reaction under observed is the synthetic material capacity under multiplying power equally in the 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; Charging/discharging voltage by the synthetic material of the embodiment of the invention 1 is very close, shows that material still has well to 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-cells and the graph of a relation of cycle-index; Wherein show with this synthetic material as the circulation when the 5C charge-discharge magnification of the electrochemical cell of anode material; After 850 all 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-cells under different multiplying synthetic among embodiment 1 and the embodiment 2.
Embodiment
Below in conjunction with specific embodiment such scheme is further specified.Should be understood that these embodiment are used to the present invention is described and are not limited to limit scope of the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Introduce and general introduction
The present invention by way of example but not the mode that provides restriction describe.It should be noted, may not be meant with a kind of embodiment " " described in the disclosure file or " a kind of " execution mode, and be meant have at least a kind of.
Hereinafter will be described various aspects of the present invention.Yet it is obvious that for those of skill in the art, can come embodiment of the present invention in only some or all of aspects according to the present invention.For purposes of illustration, this paper provides concrete numbering, material and configuration, so that people can thoroughly understand the present invention.Yet for those of skill in the art will it is obvious that, the present invention need not concrete details and can implement.In other examples, the present invention is obscure to omit or has simplified well-known characteristic in order not make.
Various operations as the step of a plurality of separations and describe successively, and are explained to help most understanding mode of the present invention; Yet, should in-order description be interpreted as that these operations of hint must depend on order.
To various execution modes be described according to the reactant of type species.For those of skill in the art will it is obvious that, the present invention can use different types of reactant of any amount to implement, and is not those reactants that provide for the purpose of illustration and here.In addition, also will it is obvious that, the present invention is not limited to any specific mixing example.
Embodiment 1Li
4Ti
5O
12Synthesizing of/C composite anode active material
In a kind of embodiment of the present invention, Li
4Ti
5O
12/ C composite material is synthetic by following process:
(1) weighing 1288g Li
2CO
3, 3480gTiO
2And 286gPVA, with load weighted raw materials mix, PVA is uniformly dispersed in raw material.Change in the high-energy mills, add the grinding of 35L water and obtain the presoma suspension-turbid liquid after 3 hours.
(2) drying obtains presoma under 110 ℃ of conditions.
(3) presoma is calcined under 2 hours 15 minutes the condition of insulation in 800 ℃ of following N2 in calciner, product obtains the Li of grey black look after pulverizing and hierarchical processing
4Ti
5O
12/ C composite material.
Embodiment 2Li
4Ti
5O
12Synthesizing of negative active core-shell material
In a kind of embodiment of the present invention, Li
4Ti
5O
12Material is synthetic by following process:
(1) weighing 1288g Li
2CO
3, 3480gTiO
2And 286gPVA, with load weighted raw materials mix, PVA is uniformly dispersed in raw material.Change in the high-energy mills, add the grinding of 35L water and obtain the presoma suspension-turbid liquid after 3 hours.
(2) drying obtains presoma under 110 ℃ of conditions.
(3) with presoma in the push-plate type calciner at 800 ℃ of following N
2Calcine under 15 minutes the condition of middle insulation, in 800 ℃ of following air, calcine under 2 hours the condition of insulation then.Product obtains the Li of white after pulverizing and hierarchical processing
4Ti
5O
12Negative material.
Fig. 1 shows the synthesis technique sketch map of material in the push-plate type calciner of the embodiment of the invention 2, and wherein precursor mixture is promoted mainly plate earlier and is transported to A stove N
2Carry out calcining in 15 minutes in the atmosphere, pushed back plate then and be transported in the B stove logical outside air and carry out calcining in 2 hours.
Li
4Ti
5O
12Or Li
4Ti
5O
12The chemical property of/C composite anode materials is realized through the commodity in use button cell.At first anode material is prepared on the Copper Foil with PVDF and super P carbon.The lithium metal is as negative electrode, and 1.3M LiPF
6(in EC/DMC, 1:1 (volume ratio)) is as electrolyte.
Fig. 2 shows embodiment 1 synthetic material and conventional solid-state method synthetic material, and embodiment 1 is with respect to the high rate capability contrast of solid phase reaction method during specimen under 5C (A) and 10C (B) condition respectively, and the capacity high magnification that is obtained by traditional solid phase reaction under observed is the synthetic material capacity under multiplying power equally in the 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; Charging/discharging voltage by the synthetic material of the embodiment of the invention 1 is very close, shows that material still has well to 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-cells under different multiplying synthetic among embodiment 1 and the embodiment 2; Can find out that embodiment 1 is very close with 2 synthetic material electrochemical performances; It should be noted that; Embodiment 2 has consumed inert atmosphere still less than embodiment 1, therefore on the technology cost, has more advantage.
Fig. 4 is the capacity of embodiment 1 synthetic material lithium titanate 2032 half-cells and the graph of a relation of cycle-index; Wherein show with this synthetic material as the circulation when the 5C charge-discharge magnification of the electrochemical cell of anode material; After 850 all 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-cells under different multiplying
This shows Li by the present invention's preparation
4Ti
5O
12And Li
4Ti
5O
12/ C negative material the lithium titanate material synthetic with respect to conventional solid-state method has excellent chemical property, and be especially particularly outstanding on high magnification and cycle performance.
In sum, the invention provides the nanoscale metatitanic acid cathode of lithium manufacture of materials technology that a kind of low cost and product cut size are evenly distributed.Through reduce the reaction number of phases and on the active cathode material that generates original position be coated with last layer carbonaceous conductive layer and reached with the technical method that improves material specific capacity to suppress that crystal is grown up and in follow-up process treatment process, to select to remove the carbonaceous conductive layer that nanoscale between the reactant mixes and the negative material that generates remains on nano-scale.The negative pole lithium titanate material of method production can overcome cost and material granule size and the homogeneity drawback that exists in traditional high temperature solid-state method and the sol-gal process simultaneously thus; Not only abundant raw materials is inexpensive; Technical process is simple, reacts controlled, and the production and processing time consumption and energy consumption is low; And product is even at nanoscale and narrowly distributing because of particle size range, therefore has excellent chemical property.Therefore it is low to the invention provides a kind of integrated cost; Function admirable and being easy to realizes method and the electrode and the battery of the production lithium titanate anode material of industrialization, and this technology helps widening the application prospect of lithium ion battery at the power transport field of the electrical network energy storage that requires overlength cycle life and security requirement height and fast charging and discharging.
The above specific embodiment only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement or replacement, these improvement or replacement also should be regarded as protection scope of the present invention.
Claims (10)
1. method of producing lithium ion cell nano level negative material, said lithium ion cell nano level negative material is selected from Li
4Ti
5O
12Negative material or Li
4Ti
5O
12/ C composite negative pole material is characterized in that said method comprising the steps of:
(1), fully mixes lithium salts presoma, TiO under the condition that the aqueous solution or solvent exist at water
2And carbon matrix precursor obtains the presoma suspension-turbid liquid;
(2) grind the presoma suspension-turbid liquid;
(3) dry presoma suspension-turbid liquid obtains precursor mixture;
(4) in inert atmosphere, perhaps precursor mixture is calcined then by elder generation in air in inert atmosphere;
(5) calcined product is pulverized and the classified lithium ion cell nano level negative material that finally obtains.
2. method according to claim 1 is characterized in that said lithium salts presoma is selected from Li
2CO
3, Li
2C
2O
4, LiOH, LiCH
3The combination in any of one or more among the COO.
3. method according to claim 1 is characterized in that said carbon matrix precursor is selected from 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, gathers hydracrylic acid, poly butyric ester, gathers hydroxypentanoic acid, gathers hydroxycaproic ester, gathers-3-Hydroxyoctanoic acid ester, gathers-one or more combination in any of 3-hydroxy phenyl valeric acid and gathering-3-hydroxy phenyl caproic acid.
4. method according to claim 1 is characterized in that said solvent is selected from isopropyl alcohol, acetone or deionized water.
5. method according to claim 1 is characterized in that said TiO
2Selecting structure for use is one or both mixtures in sharp titanium stone type or the rutile-type.
6. method according to claim 1 is characterized in that baking temperature is controlled between 100 ℃ ~ 220 ℃ in the said method.
7. method according to claim 1 is characterized in that the temperature of calcining precursor mixture in the said method is controlled between 400 ℃ ~ 1200 ℃, and calcination time is 1 ~ 6 hour.
8. a negative material that is used for electrochemical cell is selected from Li
4Ti
5O
12Negative material or Li
4Ti
5O
12/ C composite negative pole material, it forms technology and may further comprise the steps:
(1) mixes lithium salts presoma, TiO
2And the soluble carbon presoma obtains the presoma suspension-turbid liquid;
(2) grind the presoma suspension-turbid liquid;
(3) dry presoma suspension-turbid liquid obtains precursor mixture;
(4) calcining precursor mixture;
(5) pulverize and the classification calcined product after finally obtain being used for the negative material of electrochemical cell.
9. method according to claim 8 is characterized in that in the said method what the calcining precursor mixture carried out all the time in inert atmosphere, perhaps earlier in inert atmosphere, in air, carry out then.
10. electrochemical cell comprises:
(1) anode, wherein anode adopts by the described negative material that is used for electrochemical cell of claim 8.
(2) electrolyte;
(3) negative electrode;
(4) barrier film.
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Cited By (7)
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| CN102997651A (en) * | 2012-11-30 | 2013-03-27 | 龙能科技（苏州）有限公司 | Pusher furnace for preparing lithium titanate negative electrode materials of lithium ion battery and method |
| 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 |
| CN113707871A (en) * | 2021-09-02 | 2021-11-26 | 和也健康科技有限公司 | Preparation of nanobelt lithium titanate @ stone needle composite fiber material, product and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101428851A (en) * | 2008-12-04 | 2009-05-13 | 上海大学 | Process for producing lithium ion battery negative pole material of lithium titanate |
| CN102244234A (en) * | 2011-05-31 | 2011-11-16 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of carbon-coated niobium-doped nano-lithium titanate material |
| 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 |
-
2012
- 2012-09-13 CN CN201210337220.4A patent/CN102832382B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102244234A (en) * | 2011-05-31 | 2011-11-16 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of carbon-coated niobium-doped nano-lithium titanate material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102997651A (en) * | 2012-11-30 | 2013-03-27 | 龙能科技（苏州）有限公司 | Pusher furnace for preparing lithium titanate negative electrode materials of lithium ion battery and method |
| 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 |
| CN113707871A (en) * | 2021-09-02 | 2021-11-26 | 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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