CN101471439A - Composite material for lithium ion battery cathode and preparation method and cathode and battery - Google Patents

Composite material for lithium ion battery cathode and preparation method and cathode and battery Download PDF

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Publication number
CN101471439A
CN101471439A CNA2008101792727A CN200810179272A CN101471439A CN 101471439 A CN101471439 A CN 101471439A CN A2008101792727 A CNA2008101792727 A CN A2008101792727A CN 200810179272 A CN200810179272 A CN 200810179272A CN 101471439 A CN101471439 A CN 101471439A
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composite material
lithium ion
negative pole
ion battery
scope
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K·D·开普勒
刘宏建
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Farasis Energy Inc
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Farasis Energy Inc
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention discloses a composite material used for negative electrode of lithium ion battery, a preparing method and the use thereof. The composite material has a composition showed by the following formula: Mal-Xa2-Sed1-Yd2-Cc, wherein, M is one or a plurality of components selected from Sn, Al, Pb, Sb, Si and Bi. X is one or a plurality of components selected from Cu, V, Co, Ti, Mo, Mg, W and Zn. Y is Si and/or Ge; a1, a2, d1, d2 and c represent the weight percent which is respectively taken by M, X, Se, Y and C relatively to the total weight of M, X, Se, Y and C, wherein, a1+a2 is 0.4-0.7, d1+d2 is 0.05-0.6, and c is 0.01-0.25. The range of d1/d2 is 0-1/1.4, and the range of a2/a1 is 0-1/1.5.

Description

The composite material and preparation method and negative pole and the battery that are used for lithium ion battery negative
Technical field
The negative pole and the lithium ion battery that the present invention relates to a kind of composite material that is used for lithium ion battery negative and preparation method thereof and use this composite material.
Background technology
In order to solve the restriction of existing lithium-ion battery system, carried out a large amount of research about the substitution material of exploitation standard negative pole and anodal lithium ion insertion material.The energy density of the lithium ion intermetallic negative material of many high energy energy densities (removing Al, Si, Sn, Pb, Sb, Cu-Sn, Co-Sn etc.) is twice or more times of [R.A.Huggins of graphite, e.a., Journal of the Electrochemical Society, 1981.128:p.725].The intermetallic compound base negative pole particularly has the nanoscale pattern, may produce very big improvement to energy density, fail safe and the cost of lithium ion battery.However, when lithium ion circulation time inside and outside material, the problem that nearly all intermetallic compound negative pole system all exists volumetric expansion, capacitance loss and impedance to increase.Use composite algorithm and particle design method to obtain huge progress to alleviating these problems, the intermetallic negative material will begin to be used for the battery of business-like high volume energy density, and these battery applications are in very little niche market.Especially, Sony has released a kind of lithium ion battery of the Sn-Co-Ti-C of use nano particle negative material.The specific capacity of this negative material may be than present graphite littler, but have significant volume capacity advantage (US2006/0121348A1) in LITHIUM BATTERY.Though obtained than much progress, this material is only being represented a small step aspect the whole potential that use the intermetallic objects system.Short another the wide industrial broad research of having given birth to of the success of this material can provide more high power capacity and better the intermetallic objects system of performance with the discriminated union exploitation, this will satisfy the demand of emerging application (for example, EV ' s, PHEVs, e-Bikes and UPS standby system) very soon.
Demonstrating significantly from the material engineering aspect, is nanoscale and the mixed and disorderly degree that increases material with the size restrictions of intermetallic compound negative pole particle, by the size ordering, can significantly improve cyclic reversibility sometimes.This minimise stress by producing in the particle, and reduce the influence that original particle expands and work in the material failure pattern.Sometimes find also that the effective method of the volumetric expansion of restriction intermetallic material is to mix in the active material mutually inactive.This method has avoided reducing the needs (this is difficult to be designed in the completed cell) of voltage limit, makes capacitance balance move to low-voltage, thereby has improved the average voltage of battery.Therefore from the composition aspect, problem becomes: what this inactive " matrix " should contain, with performance and the value that is beneficial to most all material.In some reports, used simple conductive additive,, found that special intermetallic compound can more effectively regulate lithium ion as copper and carbon.Another kind of feasible approach is included in the lithium ion conduction phase that forms insulation in the inter-metallic compound material, this has the effect that alleviates volumetric expansion, improve the distribution of lithium in particle, with the active phase surface of lithiumation and the reaction shielding of carrying out with electrolyte, particle insulation and capacitance loss.A this example the earliest is that (Sn is at Li for vitrifying Sn-oxide cathode material 2In the O matrix) and the more recent Li that is derived from 3The phosphatization tin base cathode material of P is a kind of ionic conduction phase in discharge process.Improve although shown the restriction on the performance, these materials still have the problem of irreversible capacity loss and cycle life, and still not by commercialization.In the phosphide system, ionic conduction phase Li 3P is unstable in the general active window of tin base cathode, has limited its feasibility.
Having proposed multiple countermeasure shows: raising intermetallic compound negative pole is based on to be modified compound-material between simple metal element (as Al, Sn and Si).An example is Cu 6Sn 5(Fe) [K.D Kepler, J.T.V., M.M.Thackeray, Electrochemical and Solid State Letters, 1999.2 (7): p.307.].
Said method can solve the problem of change in volume to a certain extent, but the cycle performance of high-capacity lithium ion cell still needs to improve.
Summary of the invention
The invention describes a kind of negative pole composite alloy material that is used for lithium ion battery of high power capacity, this negative material comprises multiple components.Negative pole composite negative pole material of the present invention is suc as formula M A1-X A2-Se D1-Y D2-C cShown in.In this formula, element or the alloy of M for can reversibly reacting with lithium ion, and in this composite material, M is as primary active ingredient.Element as M can comprise Sn, Al, Sn, Al, Pb, Sb, Si and Bi.About one aspect of the present invention, the selenium in the composite negative pole material (Se) can improve cycle life and the invertibity of active ingredient M.Selenium can be used as the stabilizer of active component M Reversible Cycle.Form Li stable, that can pass to lithium ion by reacting in position at charging for the first time and lithium ion 2The Se phase, wherein, active ingredient reversibly circulates.Li 2Se mutually in this unique character can give composite material certain stability, bigger change in volume is provided, the SEI form is minimized, and makes lithium enter the minimization of loss of intermetallic negative material.Li 2Se mutually can be further at the voltage that forms outside the voltage window that activity circulates mutually more than the 1V, thereby keep stablizing when active material and lithium ion are reversibly reacted.About another aspect of the present invention, according to the general formula of anode material, anode material may further include Si and/or the Ge that is represented by Y.These elements can be used as and strengthen the Li that original position forms 2The lithium ion conductive of Se phase.The Li of doped with Ge and Si 2The Se glassy phase is in the news and compares Li 2Se has higher lithium ion conductive.(Michel-Lledos，V.，A.Pradel，andM.Ribes，Lithium conductive selenide glasses.Eur.J.Solid State Inorg.Chem.FIELD Full Journal Title：European Journal of Solid State and InorganicChemistry，1992.29(2)：p.301-10.(Pradel，A.，et al.，Structural and electricalcharacterization of glasses in the system lithium selenide-silicon selenide(Li2Se-SiSe2)by 29Si MAS NMR and Raman spectroscopy.Solid State IonicsFIELD Full Journal Title：Solid State Ionics，1992.53-56(Pt.2)：p.1187-93).
According to another aspect of the present invention, composite material can further include inactive metallic element X, with dilution activity phase, overall volume expansion is minimized, and reduces the reversible capacity loss of circulation for the first time.Element X can be for being selected among Cu, V, Co, Ti, Mo, Mg, W and the Zn one or more.According to a further aspect in the invention, anode material comprises carbon.Carbon can be simplified the synthetic of compound, improves the electric conductivity between composite particles.Compared with the prior art, anode material of the present invention provides higher capacity and cyclic reversibility.
In order to improve the cycle performance of high-capacity lithium ion cell, an object of the present invention is to provide a kind of composite material that is used for lithium ion battery negative, this composite material contains the composition shown in the following formula:
M a1-X a2-Se d1-Y d2-C c
Wherein, M is selected among Sn, Al, Pb, Sb, Si and the Bi one or more;
X is selected among Cu, V, Co, Ti, Mo, Mg, W and the Zn one or more;
Y is Si and/or Ge;
A1, a2, d1, d2 and c represent the total weight with respect to M, X, Se, Y and C, the weight ratio that M, X, Se, Y and C are shared separately, wherein, a1+a2 is 0.4-0.7, and d1+d2 is 0.05-0.6, and c is 0.01-0.25, the scope of d2/d1 is 0 to 1/1.4, and the scope of a2/a1 is 0 to 1/1.5.
A kind of preferred embodiment in, M is Sn, Y is Si.
A kind of preferred embodiment in, d2/d1 is 0, perhaps scope is 0.05/1.4 to 1/1.4.
A kind of preferred embodiment in, a2/a1 is 0, perhaps scope is 0.05/1.5 to 1/1.5.
A kind of preferred embodiment in, the median particle diameter (D of this composite material 50) be 5 nanometers to 15 micron, be preferably 0.01 micron-1 micron.According to preferred embodiment this, this composite material is a nanoscale, thereby can restricted volume variation effect, further improves cycle performance.
A kind of preferred embodiment in, this composite material also contains Li, the weight ratio of Li and Se is 0.05-2.This preferred embodiment in because Li 2The high balanced voltage that Se forms mutually (with respect to the about 2V of lithium), elements doped lithium in these materials to be pre-formed the ionic conduction phase, may be eliminated any relative reversible loss.Though Li 2Se is to water sensitive, but more stable than other lithium inter-metallic compound material (LiSb, LiSn etc.) at 2.0V, other lithium inter-metallic compound material can not be carried out the normal electrode manufacturing technology then by pre-lithiaization to be handled.
Another object of the present invention provides a kind of method for preparing above-mentioned material, and this method comprises the step that M, X, Se, Y and C are mixed and grind, and wherein, the consumption of M, X, Se, Y and C makes the composite material that obtains contain the composition shown in the following formula:
M a1-X a2-Se d1-Y d2-C c
Wherein, M is selected among Sn, Al, Pb, Sb, Si and the Bi one or more;
X is selected among Cu, V, Co, Ti, Mo, Mg, W and the Zn one or more;
Y is Si and/or Ge;
A1, a2, d1, d2 and c represent the total weight with respect to M, X, Se, Y and C, the weight ratio that M, X, Se, Y and C are shared separately, wherein, a1+a2 is 0.4-0.7, and d1+d2 is 0.05-0.6, and c is 0.01-0.25, the scope of d2/d1 is 0 to 1/1.4, and the scope of a2/a1 is 0 to 1/1.5.
M, X, Se, Y and C can be respectively simple substance form and provide, and perhaps provide to contain the alloy form that is selected from two or more elements among M, X, Se, Y and the C.
Simple substance C can be any conventionally form, is preferably to be selected from graphite, carbon black and the acetylene black one or more.
Described grinding can be used this area any Ginding process commonly used, as long as raw material can be ground equably.For example, can in planetary ball mill, raw material be ground.Can adjust the condition of grinding as required, as long as can obtain the composite material that median particle diameter is 5 nanometers to 15 micron.A kind of preferred embodiment in, in planetary ball mill, ground 5-50 hour with the speed of 100-500rpm.
A kind of preferred embodiment in, method of the present invention also is included in the process of lapping step that adds Li, making the Li that contains in the described composite material and the weight ratio of Se is 0.05-2.
Another object of the present invention provides a kind of negative pole that is used for lithium ion battery, changes negative pole and contains composite material provided by the invention, and this battery is being lower than Li after being initialized to step 2Reversibly circulation in the voltage window scope of the formation voltage of Se phase (formation voltage).
Another object of the present invention provides a kind of lithium ion battery that contains composite material of the present invention.Except composite material of the present invention is used as negative material, other part of this secondary lithium battery can be that this area is commonly used.
With compare by the lithium ion battery of existing negative material preparation, use the lithium ion battery of composite material of the present invention to have the capacity of better cycle ability and Geng Gao.
Description of drawings
Fig. 1 represents the discharge capacity of several negative materials and the relation of cycle-index;
Fig. 2 is the chart of the relation of each efficient that circulates of expression and cycle-index;
Fig. 3 represents the discharge capacity of several negative materials and the relation of cycle-index;
Fig. 4 represents the discharge weight ratio capacity of the intermetallic negative material of various Sn of containing and Se;
Fig. 5 represents the voltage curve of Sn-SeSi-C (50:40:10) negative material;
Fig. 6 represents the weight ratio capacity of a series of negative materials and the relation of cycle-index;
When Fig. 7 is illustrated in density and is 5g/cc, the comparison of the volume and capacity ratio of material and carbon between best metal.
Embodiment
Below, will present invention is described by embodiment.But it will be appreciated by those skilled in the art that provides these embodiment just for the purpose of description, rather than in order to limit the scope of the invention.
Embodiment
Table 1: intermetallic composite negative pole material
Numbering Symbol in the accompanying drawings Voltage window (V) Form (weight %) Grinding rate (rpm)/milling time (h) Granular size, D 10 (um) Granular size, D 50 (um) Granular size. D 90(um)
Embodiment 1 Sn-Se-C 0-1.0 50％Sn-40％Se-10％C 225/35 0.2 2.83 6.3
Comparative Examples 1 Sn-Co-C-Ti 0-1.0 52.5％Sn-33.5％Co-10％C-4％Ti 225/40 0.1 1.24 2.79
Embodiment 2 Sn-Se-Co-C 0-1.0 50％Sn-20％Se-20％M-10％C． M＝Co 225/35 0.15 1.81 4.2
Embodiment 3 Sn-Se-V-C 0-1.0 50％Sn-20％Se-20％M-10％C.M＝V 225/25 0.88 4.25 8.26
Embodiment 4 Sn-SeSi-C 0-1.0 50％Sn-40％(S 0.4Se 1.4)-10％C 225/40 0.1 1.56 4.47
Embodiment 5 Sn-CoVCuTi-SeSi -C 0-1.0 50％Sn-25％(CoVCuTi)-15％(Si0.4S e 1.4)-10％C 225/50 0.1 0.87 2.45
Comparative Examples 2 Sn-CoVCuTi-C 0-1.0 50％Sn-40％(CoVCuTi)-10％C 225/15 1.51 5.58 9.91
Comparative Examples 3 Sn-C 0-1.0 80％Sn-20％C 225/15 1.6 6.2 9.8
Comparative Examples 4 (Se1.4Si0.4)-C 0-1.0 80％(Se 1.4Si 0.4)-20％C 225/25 0.5 2.68 5.8
Embodiment 1
Sn-Se-C intermetallic composite negative pole material
According to table 1 listed composition and grinding condition (grinding rate/milling time), by using high-energy planetary formula ball mill various simple substance materials are carried out mechanical alloying, make Sn-Se-C intermetallic composite negative pole material.
Be specially: according to weight percentage is 50%Sn-40%Se-10%C, take by weighing simple substance tin (Sn, Alfa Aesar), selenium (Se, Alfa Aesar), carbon (C, Osaka Gas), and dry mixing premixed 12 hours (Wheaton Modular Cell Production Roller Apparatus, Model III).80 these premixed Sn-Se-C mixtures of gram are transferred in four stainless cylinder of steels, and there are 400 gram stainless steel balls (diameter is 10mm) each the inside.The stainless cylinder of steel of sealing is placed in the high-energy planetary formula ball mill (ND7-2L planetary ball mill, Tianzhun Co., Ltd),, open stainless cylinder of steel after being cooled to room temperature then with the rotating speed mixed grinding of 225rpm 25 hours.
This material is collected, is crossed the sieve (Octagon 200 Test Sieve Shaker) of 56-90 micron, the particle size that measures as shown in table 1 (LA500, Horiba, Ltd.).Prepare electrode then: the active material with 86%, 10% Kynoar adhesive (Solvey) and 4% carbon black (Osaka Gas) form slurry with the N-methyl pyrrolidone, then this slurry are coated on the Copper Foil.From these coating directions electrode is punched, use as to the lithium paper tinsel of electrode, porous polyethylene barrier film with as the LiPF of the 1M of electrolyte 6-EC/DEC (ethylene carbonate/diethyl carbonate) makes CR2032 type button cell.Use these CR2032 button cells carry out electro-chemical test (CT2001A, LAND Battery TestSystem, Kingnuo Electronic Co., Ltd.).
Comparative Examples 1
Se-Co-C-Ti intermetallic composite negative pole material
Prepare intermetallic Se-Co-C-Ti composite negative pole material with the method identical with embodiment 1, different is that weight consists of 52.5%Sn-33.5%Co-10%-C4%Ti, and the stainless cylinder of steel that will cool off is transferred in the glove box that is filled with argon gas.In glove box, collect this material, transfer to then in the vacuum furnace, air is entered lentamente.
Embodiment 2
Sn-Se-M-C intermetallic composite negative pole material (M=Co)
Prepare intermetallic Sn-Se-M-C composite negative pole material with the method identical with Comparative Examples 1 described method, different is that weight consists of: 50%Sn-20%Se-20%M-10%C, wherein, M=Co.
Embodiment 3
Sn-Se-M-C intermetallic composite negative pole material (M=V)
Prepare intermetallic Sn-Se-M-C composite negative pole material with the method identical with Comparative Examples 1 described method, different is that weight consists of: 50%Sn-20%Se-20%M-10%C, wherein, M=V.
Embodiment 4
Sn-SeSi-C intermetallic composite negative pole material
Prepare intermetallic Sn-SeSi-C composite negative pole material with the method identical with Comparative Examples 1 described method, different is that weight consists of: 50%Sn-40% (Si 0.4Se 1.4)-10%C.
Embodiment 5
Sn-CoVCuTi-SeSi-C intermetallic composite negative pole material
Prepare intermetallic Sn-CoVCuTi-SeSi-C composite negative pole material with the method identical with Comparative Examples 1 described method, different is that weight consists of: 50%Sn-25% (CoVCuTi)-15% (Si 0.4Se 1.4)-10%C.In above-mentioned composition, a kind of specific sample contains 11.55% Co, 7.60% V, 4.15% Cu and 1.70% Ti.
Comparative Examples 2
Sn-CoVCuTi-C intermetallic composite negative pole material
Prepare intermetallic Sn-CoVCuTi-C composite negative pole material with the method identical with Comparative Examples 1 described method, different is that weight consists of: 50%Sn-40% (CoVCuTi)-10%C.In above-mentioned composition, a kind of specific sample contains 10% Co, 23% V, 2% Cu and 5% Ti.
Comparative Examples 3
Sn-C intermetallic composite negative pole material
Prepare intermetallic Sn-C composite negative pole material with the method identical with Comparative Examples 1 described method, different is that weight consists of: 80%Sn-20%C.
Comparative Examples 4
(Se 1.4Si 0.4)-C intermetallic composite negative pole material
Prepare intermetallic (Se with the method identical with Comparative Examples 1 described method 1.4Si 0.4)-C composite negative pole material, different is that weight consists of: 80% (Se 1.4Si 0.4)-20%C.
With embodiment 1 described method the intermetallic composite negative pole material that the foregoing description and Comparative Examples make is carried out electro-chemical test.Concrete outcome is listed in Fig. 1-Fig. 5.
Fig. 1 represents the discharge capacity of different negative materials and the relation of cycle-index.The Sn-C material is used as the baseline material to compare.Reported Sn-Co-Ti-C (52.5-33.5-4-10 weight %) compound in the document, its composition is similar to the composition of existing commercialization negative material.Sn-Se-C (50-40-10 weight %) compound is the embodiment of material of the present invention.The cycle period of material of the present invention is more a lot of than the length of other material, and more stable.
This is more obvious expressively in Fig. 2, and Fig. 2 is the chart of the relation of each efficient that circulates of expression and cycle-index.The Sn-Se-C compound is higher than the efficient of business-like compound, illustrates that in the completed cell of using for the limited positive pole of lithium amount, this battery is longer than the circulation timei of the battery that uses other intermetallic compound.Also expressed other compound of the present invention among the figure, comprised Sn-Se-Co-C (50-20-20-10 weight %) and Sn-Se-V-C (50-20-20-10 weight %), these compounds have all shown better stabilised efficiency in the battery circulation.
Fig. 3 represents how to reduce the irreversible capacity loss relevant with material of the present invention by adding the 4th kind of element (being cobalt herein), keep big capacity and stable Reversible Cycle simultaneously.
Fig. 4 represents the discharge weight ratio capacity of the intermetallic compound negative material of various Sn of containing and Se.The cycle life of material of the present invention (Sn-SeSi-C) is than other material (Sn-C or (Se 1.4Si 0.4)-C) longer, more stable.
Fig. 5 represents the voltage curve of Sn-SeSi-C (50:40:10) negative material.Observe voltage platform at 1.2V in the first time in the charging cycle, the Se composition of this and composite material forms Li 2The reacting phase correspondence of Se phase.After first charging cycle, negative pole is being lower than Li 2The voltage window of the formation voltage 1.2V of Se phase reversibly circulates, and the interior electro-chemical activity of battery is stopped.
Fig. 6 represents the weight ratio capacity of a series of negative materials and the relation of circulation.The cycle life of material of the present invention (Sn-CoVCuTi-SeSi-C) is longer, more stable than other material (Sn-CoVCuTi-C or Sn-C).
When Fig. 7 is illustrated in density and is 5g/cc, the comparison of the volume and capacity ratio of compound-material and carbon between best metal.

Claims (13)

1, a kind of composite material that is used for lithium ion battery negative, this composite material contains the composition of forming shown in the following formula:
M a1-X a2-Se d1-Y d2-C c
Wherein, M is selected among Sn, Al, Pb, Sb, Si and the Bi one or more;
X is selected among Cu, V, Co, Ti, Mo, Mg, W and the Zn one or more;
Y is Si and/or Ge;
A1, a2, d1, d2 and c represent the total weight with respect to M, X, Se, Y and C, the weight ratio that M, X, Se, Y and C are shared separately, wherein, a1+a2 is 0.4-0.7, and d1+d2 is 0.05-0.6, and c is 0.01-0.25, the scope of d2/d1 is 0 to 1/1.4, and the scope of a2/a1 is 0 to 1/1.5.
2, composite material according to claim 1, wherein, M is Sn, Y is Si.
3, composite material according to claim 2, wherein, the scope of a2/a1 is 0-1/1.5, and d2/d1 is 0, and X is selected among Cu, V, Co, Ti and the Mo one or more.
4, composite material according to claim 2, wherein, a2/a1 is 0, d2/d1 is 0.
5, composite material according to claim 1, wherein, the scope of d2/d1 is 0.05/1.4 to 1/1.4.
6, composite material according to claim 1, wherein, the scope of a2/a1 is 0.05/1.5 to 1/1.5.
7, composite material according to claim 1, wherein, the median particle diameter of this composite material is 5 nanometers to 15 micron.
8, composite material according to claim 1, wherein, this composite material also contains Li, and the weight ratio of Li and Se is 0.05-2.
9, the preparation method of the described composite material of claim 1, this method comprise the step that M, X, Se, Y and C are mixed and grind, and wherein, the consumption of M, X, Se, Y and C makes the composite material that obtains have the composition shown in the following formula:
M a1-X a2-Se d1-Y d2-C c
Wherein, M is selected among Sn, Al, Pb, Sb, Si and the Bi one or more;
X is selected among Cu, V, Co, Ti, Mo, Mg, W and the Zn one or more;
Y is Si and/or Ge;
A1, a2, d1, d2 and c represent the total weight with respect to M, X, Se, Y and C, the weight ratio that M, X, Se, Y and C are shared separately, wherein, a1+a2 is 0.4-0.7, and d1+d2 is 0.05-0.6, and c is 0.01-0.25, the scope of d2/d1 is 0 to 1/1.4, and the scope of a2/a1 is 0 to 1/1.5.
10, method according to claim 9, wherein, described grinding is included in the planetary ball mill with the speed of 100-500rpm and ground 5-50 hour.
11, method according to claim 9, wherein, this method also is included in the process of lapping step that adds Li, and making the Li that contains in the described composite material and the weight ratio of Se is 0.05-2.
12, a kind of negative pole of lithium ion battery, wherein, this negative pole contains any described composite material among the claim 1-8, and described composite material is reversibly circulation in voltage window in lithium ion battery, and this voltage window is no more than the response voltage of the Se composition in the composition.
13, a kind of lithium ion battery, the negative pole of this lithium ion battery contain any described composite material among the claim 1-8.
CNA2008101792727A 2007-12-04 2008-12-04 Composite material for lithium ion battery cathode and preparation method and cathode and battery Pending CN101471439A (en)

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CN104471758A (en) * 2012-05-11 2015-03-25 株式会社三德 Negative electrode for lithium-ion secondary battery
CN117199506A (en) * 2023-11-08 2023-12-08 宁德时代新能源科技股份有限公司 Battery monomer, preparation method thereof, battery and power utilization device
CN117199506B (en) * 2023-11-08 2024-05-10 宁德时代新能源科技股份有限公司 Battery monomer, preparation method thereof, battery and power utilization device

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104471758A (en) * 2012-05-11 2015-03-25 株式会社三德 Negative electrode for lithium-ion secondary battery
CN104471758B (en) * 2012-05-11 2017-09-12 株式会社三德 The negative pole of lithium rechargeable battery
CN117199506A (en) * 2023-11-08 2023-12-08 宁德时代新能源科技股份有限公司 Battery monomer, preparation method thereof, battery and power utilization device
CN117199506B (en) * 2023-11-08 2024-05-10 宁德时代新能源科技股份有限公司 Battery monomer, preparation method thereof, battery and power utilization device

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