CN104617254A - Composite anode material used for lithium ion batteries - Google Patents

Composite anode material used for lithium ion batteries Download PDF

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Publication number
CN104617254A
CN104617254A CN201310535550.9A CN201310535550A CN104617254A CN 104617254 A CN104617254 A CN 104617254A CN 201310535550 A CN201310535550 A CN 201310535550A CN 104617254 A CN104617254 A CN 104617254A
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negative pole
lithium ion
electrons
composite negative
mixed conductor
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申兰耀
王兆翔
陈立泉
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Institute of Physics of CAS
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Institute of Physics of CAS
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1395Processes of manufacture of electrodes based on metals, Si or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387Tin or alloys based on tin
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a composite anode material used for lithium ion batteries. The composite anode material comprises an anode active material, and an electron/ion mixed conductor material; and the anode active material is coated with the electron/ion mixed conductor material.

Description

A kind of composite negative pole material for lithium ion battery
Technical field
The present invention relates to this kind of composite negative pole material for lithium ion battery, particularly relate to a kind of negative material of silica-based and tinbase.
Background technology
Along with the exhaustion day by day of fossil energy and the day by day serious of problem of environmental pollution, find a kind of alternative clean energy resource and become more and more important.Lithium ion battery is as the chargeable secondary cell of one, because its energy density is high, self discharge is little, has extended cycle life, in the digital electronic goods such as the advantages such as green non-pollution have been widely used in notebook, mobile phone.But along with the development of electronics technology and the demand of electric automobile, it is more and more urgent that the capacity improving lithium ion battery further also becomes.
Silica-base material is because have high lithium storage content (theoretical specific capacity 4200mAh g -1), and be widely used in the negative pole of lithium ion battery, as negative active core-shell material.But in charge and discharge process, the volume of silica-base material marked change can occur, and the expansion-contraction repeatedly of volume can cause the fragmentation of based particles wherein, to make between based particles and between based particles and collector, electrical contact is deteriorated.The fresh surface that new broken based particles exposes in addition can make again electrolyte decompose, and consumes electrolyte and limited lithium source, the cycle performance of silica-base material is declined, reduces the coulombic efficiency of battery, battery capacity is decayed rapidly.These all limit the application of silica-base material in lithium ion battery.
By subtracting short grained size (as about 50nm), subtracting the change of less granular absolute volume, the Particle Breakage brought due to change in volume can be reduced.But can cause the remarkable increase of silica-base material specific area after reduction particle size, easier and electrolyte reacts, and reduces coulombic efficiency.And can agglomeration be there is in charge and discharge process, make lithium ion can not react with whole based particles, reduce the utilance of silica-base material in particle size after reducing.
The method that another kind improves the cycle performance of silica-base material at other material of based particles outer cladding (as Fe, Cu, Ni, Ti, C, SiO xdeng), the efflorescence effect brought with the change in volume cushioning based particles.Conventional clad material has electron conduction material or ion-conductive material (solid electrolyte).But the shortcoming of this kind of technology is when coating thickness is less, the isolation of the efflorescence of silicon grain or realization and extraneous electrolyte effectively can not be suppressed; When coating layer is thicker, the coating layer formed due to electron conduction material can only provide electronics, the coating layer that ion-conductive material is formed can only provide ionic conductance, the rapid electric charge transfer of the electron-ion on based particles surface can not be realized, make the high rate performance of this silicon based composite material limited, reduce the specific capacity of silica-base material.Therefore, this clad material has extremely strict restriction to thickness, higher to manufacture process requirement.
For other negative active core-shell material, the tin base cathode active material of such as conventional Fabrication of High Specific Capacitance, above problem exists too.
Summary of the invention
Therefore, the object of the invention is to the defect overcoming above-mentioned prior art, a kind of composite negative pole material for lithium ion battery is provided.
The invention provides a kind of composite negative pole material for lithium ion battery, comprise negative active core-shell material and electrons/ions mixed conductor material, wherein said negative active core-shell material is covered by described electrons/ions mixed conductor material.
According to composite negative pole material provided by the invention, wherein said electrons/ions mixed conductor material is all greater than 10 at the electronic conductivity of 25 DEG C and ionic conductivity -20s cm -1.
According to composite negative pole material provided by the invention, wherein said electrons/ions mixed conductor material is mixture, comprises electronic conductive material and ion conductive material.
According to composite negative pole material provided by the invention, described electronic conductive material be selected from carbon, metal, conducting polymer composite one or more.
According to composite negative pole material provided by the invention, described ion conductive material is mixture, comprises macromolecular material and lithium salts.
According to composite negative pole material provided by the invention, wherein said electrons/ions mixed conductor material comprises conducting polymer composite and lithium salts.
According to composite negative pole material provided by the invention, wherein said electrons/ions mixed conductor material also comprises nano-ceramic particle.
According to composite negative pole material provided by the invention, wherein said negative active core-shell material is silicon, tin, SnO 2, SnCo, SiO or FeSi.
Present invention also offers a kind of lithium ion battery comprising above-mentioned composite negative pole material.
Should in composite negative pole material provided by the invention, negative active core-shell material is wrapped in electrons/ions mixed conductor material, can prevent negative material in charge and discharge process due to Particle Breakage that the expansion-contraction of volume causes, avoid the electrical contact between particle and between particle and collector to be deteriorated, prevent particle and electrolyte contacts.Meanwhile, because electrons/ions mixed conductor material can simultaneously conduction electron and lithium ion, can ensure the rapid electric charge transfer of the electronics-lithium ion on negative active core-shell material surface, and the adjustable extent of thickness is wider, the nargin of manufacturing process is larger.
Accompanying drawing explanation
Referring to accompanying drawing, embodiments of the present invention is further illustrated, wherein:
The structural representation of the negative pole that Fig. 1 provides for embodiment 1;
In the voltage curve of 0.005-1.5V voltage range in the composite negative pole material that Fig. 2 provides for embodiment 1 after the production three weeks.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with specific embodiment, the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
The present embodiment provides a kind of preparation method of the negative pole for lithium ion battery, comprising:
1) nano silica fume and carbon nano-tube are added in DMF solvent according to mass ratio 7:1 mix;
2) by polyacrylonitrile (PAN) powder and lithium perchlorate (LiClO 4) according to mol ratio be 10:1 mixing;
3) by step 2) mixture that obtains is 2:7 ratio joins step 1 according to silica flour mass ratio) in the DMF solution that obtains, at 50 DEG C, stir into uniform sizing material;
4) this slurry is coated on the surface of the Copper Foil as collector, blade coating film forming, makes nano silica fume and collector form all even good electrical contact;
5) in vacuum drying oven, 100 DEG C of oven dry 6h remove moisture, then at 200 DEG C of heat treatment 2h, polyacrylonitrile (PAN) is cross-linked, obtains the negative pole for lithium ion battery after being down to room temperature.
The structure of the negative pole that the method that Fig. 1 illustrates to be provided by the present embodiment obtains.As shown in Figure 1, this negative pole comprises collector and coating composite negative pole material on a current collector, and this composite negative pole material is made up of negative active core-shell material and electrons/ions mixed conductor material.Wherein negative active core-shell material is silicon, and electrons/ions mixed conductor material is carbon nano-tube, polyacrylonitrile (PAN) and lithium perchlorate (LiClO 4) mixture.Wherein carbon nano-tube plays the effect of conduction electron, polyacrylonitrile (PAN) and lithium perchlorate (LiClO 4) effect of conducting lithium ions is played after mixing due to dissociation.
In the composite negative pole material provided in the present embodiment, negative active core-shell material is wrapped in electrons/ions mixed conductor material, can prevent negative material in charge and discharge process due to Particle Breakage that the expansion-contraction of volume causes, avoid the electrical contact between particle and between particle and collector to be deteriorated, prevent particle and electrolyte contacts.Meanwhile, because electrons/ions mixed conductor material can simultaneously conduction electron and lithium ion, can ensure the rapid electric charge transfer of the electronics-lithium ion on negative active core-shell material surface, and the adjustable extent of thickness is wider, the nargin of manufacturing process is larger.
Composite negative pole material prepared by the method that the present embodiment provides, in after the production three weeks, in 0.005-1.5V voltage range voltage curve as shown in Figure 2.This figure reflects the variation relation of composite negative pole material charging and discharging capacity and voltage.As shown in the figure, the first all charging and discharging capacities of this composite negative pole material are respectively 1095mAh/g, 1547mAh/g.First all irreversible capacities can ascribe the isolated Li-Si alloy etc. formed in the decomposition of electrolyte and first all charge and discharge process to.After first Zhou Fang electricity, silicon grain becomes impalpable structure, and within follow-up two weeks, charging and discharging curve is similar, shows having good stability of the composite negative pole material prepared by the method that the present embodiment provides.
In the composite negative pole material that the present embodiment provides in addition, macromolecular material containing high viscosity in the electrons/ions mixed conductor material adopted, therefore without the need to additionally adding bonding agent or only needing a small amount of bonding agent, quality and the volume fraction of negative active core-shell material in negative pole can be improved.
In order to further illustrate the performance of the composite negative pole material that the present embodiment provides, the negative pole containing this composite negative pole material is made battery.This battery utilizes lithium metal to do electrode, utilizes 1mol/LLiPF 6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (the mass ratio 1:1 of EC and DMC) as electrolyte, in an inert atmosphere (oxygen content, water content are all less than 1ppm) be assembled into battery.Carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of this battery, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the negative material that the present embodiment provides has good cycle performance.
Embodiment 2
The present embodiment provides a kind of preparation method of the negative pole for lithium ion battery.This preparation method is substantially identical with the method in embodiment 1, and the difference of the two is only polyacrylonitrile (PAN) and lithium perchlorate (LiClO 4) be 5:1 according to mol ratio.
In order to further illustrate the performance of the composite negative pole material that the present embodiment provides, utilize the method identical with embodiment 1 that the negative pole containing this composite negative pole material is made battery.Carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of this battery, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the negative material that the present embodiment provides has good cycle performance.
Embodiment 3
The present embodiment provides a kind of preparation method of the negative pole for lithium ion battery, and this preparation method is substantially identical with the method in embodiment 1, and the difference of the two is only that the method making polyacrylonitrile (PAN) crosslinked is different.In the present embodiment, after 100 DEG C of oven dry 6h remove moisture in vacuum drying oven, carry out ultraviolet light irradiation 30min and be cross-linked to make polyacrylonitrile (PAN).
In order to further illustrate the performance of the composite negative pole material that the present embodiment provides, utilize the method identical with embodiment 1 that the negative pole containing this composite negative pole material is made battery.Carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of this battery, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the negative material that the present embodiment provides has good cycle performance.
Embodiment 4
The present embodiment provides a kind of preparation method of the negative pole for lithium ion battery, this preparation method is substantially identical with the method in embodiment 1, the difference of the two is only polyacrylonitrile (PAN) powder to replace to polyethylene oxide powder (PEO), by lithium perchlorate (LiClO 4) replace to two (trifluoromethyl) sulfimide lithium (LiTFSI).The mol ratio of polyethylene oxide powder (PEO) and LiTFSI is 10:1.
In the composite negative pole material that the present embodiment provides, electrons/ions mixed conductor material is the mixture of carbon nano-tube, poly(ethylene oxide) (PEO) and LiTFSI.The effect of conducting lithium ions is wherein played after poly(ethylene oxide) (PEO) and LiTFSI mixing due to dissociation.
In the composite negative pole material that the present embodiment provides in addition, polyethylene oxide powder (PEO) containing high viscosity in the electrons/ions mixed conductor material adopted, therefore without the need to additionally adding bonding agent or only needing a small amount of bonding agent, quality and the volume fraction of negative active core-shell material in negative pole can be improved.
In order to further illustrate the performance of the composite negative pole material that the present embodiment provides, the negative pole containing this composite negative pole material is made battery.This battery utilizes lithium metal to do electrode, utilize 1mol/LLiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (the mass ratio 1:1 of EC and DMC) as electrolyte, in an inert atmosphere (oxygen content, water content are all less than 0.1ppm) be assembled into battery.Carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of this battery, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the negative material that the present embodiment provides has good cycle performance.
Embodiment 5
The present embodiment provides a kind of preparation method of the negative pole for lithium ion battery, comprising:
1) nano silica fume, carbon nano-tube and nanosized SiO_2 are added in DMF solvent according to mass ratio 7:0.8:0.2 mix;
2) be 10:1 mixing by polyethylene oxide powder (PEO) and LiTFSI according to mol ratio;
3) by step 2) mixture that obtains is 2:7 ratio joins step 1 according to silica flour mass ratio) in the DMF solution that obtains, at 50 DEG C, stir into uniform sizing material;
4) this slurry is coated on the surface of the Copper Foil as collector, blade coating film forming, makes nano silica fume and collector form all even good electrical contact;
5) in vacuum drying oven, 100 DEG C of oven dry 6h remove moisture, obtain the negative pole for lithium ion battery after being down to room temperature.
The negative pole that the present embodiment provides comprises collector and coating composite negative pole material on a current collector.This composite negative pole material is made up of negative active core-shell material and electrons/ions mixed conductor material.Wherein negative active core-shell material is silicon, and electrons/ions mixed conductor material is carbon nano-tube, SiO 2, poly(ethylene oxide) (PEO) and LiTFSI mixture.Wherein carbon nano-tube plays the effect of conduction electron.Play the effect of conducting lithium ions due to dissociation after poly(ethylene oxide) (PEO) and LiTFSI mix.SiO 2add the conduction that can strengthen lithium ion.
In the composite negative pole material provided in the present embodiment, negative active core-shell material is wrapped in electrons/ions mixed conductor material, can prevent negative material in charge and discharge process due to Particle Breakage that the expansion-contraction of volume causes, avoid the electrical contact between particle and between particle and collector to be deteriorated, prevent particle and electrolyte contacts.Meanwhile, because electrons/ions mixed conductor material can simultaneously conduction electron and lithium ion, can ensure the rapid electric charge transfer of the electronics-lithium ion on negative active core-shell material surface, and the adjustable extent of thickness is wider, the nargin of manufacturing process is larger.
In order to further illustrate the performance of the composite negative pole material that the present embodiment provides, utilize the method identical with embodiment 4 that the negative pole containing this composite negative pole material is made battery.Carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of this battery, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the negative material that the present embodiment provides has good cycle performance.
Embodiment 6-9
Embodiment 6-9 provides a kind of preparation method of the negative pole for lithium ion battery respectively, and these preparation methods are substantially identical with the method in embodiment 5, and their difference is only Nano-meter SiO_2 2replace to Al respectively 2o 3(embodiment 6), MgO(embodiment 7), ZrO 2(embodiment 8), Li 3pO 4-xn x(embodiment 9).These nano ceramic material particles add the conduction that can strengthen lithium ion.
In order to further illustrate the performance of the composite negative pole material that embodiment 6-9 provides, the negative pole containing this composite negative pole material utilizing the method identical with embodiment 5 to be provided by embodiment 6-9 makes battery respectively.Carry out charge-discharge test to these batteries, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that these negative materials that embodiment 6-9 provides have good cycle performance.
Embodiment 10-17
Embodiment 10-17 provides a kind of preparation method of the negative pole for lithium ion battery respectively, these preparation methods are substantially identical with the method in embodiment 4, their difference is only polyethylene oxide powder (PEO) to replace to polyethylene (PE) (embodiment 10) respectively, polypropylene (PP) (embodiment 11), polymethyl methacrylate (PMMA) (embodiment 12), Kynoar (PVDF) (embodiment 13), polyvinyl chloride (PVC) (embodiment 14), polyimides (PI) (embodiment 15), polyamidoimide (PAI) (embodiment 16), polyamide (PA) (embodiment 17).
In order to further illustrate the performance of the composite negative pole material that embodiment 10-17 provides, the negative pole containing this composite negative pole material utilizing the method identical with embodiment 5 to be provided by embodiment 10-17 makes battery respectively.Carry out charge-discharge test to these batteries, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that these negative materials that embodiment 10-17 provides have good cycle performance.
Embodiment 18-22
Embodiment 18-22 provides a kind of preparation method of the negative pole for lithium ion battery respectively, and these preparation methods are substantially identical with the method in embodiment 4, and their difference is only LiTFSI to replace to LiPF respectively 6(embodiment 18), LiBF 4(embodiment 19), LiClO 4(embodiment 20), LiFSI(embodiment 21), LiBOB(embodiment 22).
In order to further illustrate the performance of the composite negative pole material that embodiment 18-22 provides, the negative pole containing this composite negative pole material utilizing the method identical with embodiment 4 to be provided by embodiment 18-22 makes battery respectively.Carry out charge-discharge test to these batteries, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that these negative materials that embodiment 18-22 provides have good cycle performance.
Embodiment 23
The present embodiment provides a kind of preparation method of the negative pole for lithium ion battery, comprising:
1) nano silica fume, carbon nano-tube are added in DMF solvent according to mass ratio 7:1 mix;
2) polyethylene (PE) powder, poly(ethylene oxide) (PEO) powder and LiTFSI are mixed according to mol ratio 5:5:2;
3) by step 2) mixture that obtains is 2:7 ratio joins step 1 according to silica flour mass ratio) in the DMF solution that obtains, at 50 DEG C, stir into uniform sizing material;
4) this slurry is coated on the surface of the Copper Foil as collector, blade coating film forming, makes nano silica fume and collector form all even good electrical contact;
5) in vacuum drying oven, 100 DEG C of oven dry 6h remove moisture, obtain the negative pole for lithium ion battery after being down to room temperature.
In order to further illustrate the performance of the composite negative pole material that embodiment 23 provides, the negative pole containing this composite negative pole material utilizing the method identical with embodiment 5 embodiment 23 to be provided makes battery.Carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of this battery, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the negative material that embodiment 23 provides has good cycle performance.
Embodiment 24-31
Embodiment 24-31 provides a kind of preparation method of the negative pole for lithium ion battery respectively, these preparation methods are substantially identical with the method in embodiment 23, their difference is only polyethylene (PE) powder wherein to replace with polypropylene (PP) (embodiment 24) respectively, polymethyl methacrylate (PMMA) (embodiment 25), Kynoar (PVDF) (embodiment 26), polyvinyl chloride (PVC) (embodiment 27), polyimides (PI) (embodiment 28), polyamidoimide (PAI) (embodiment 29), polyamide (PA) (embodiment 30), polyacrylic acid (PAA) (embodiment 31).
In order to further illustrate the performance of the composite negative pole material that embodiment 24-31 provides, the negative pole containing this composite negative pole material utilizing the method identical with embodiment 6 to be provided by embodiment 24-31 makes battery respectively.Carry out charge-discharge test to these batteries, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that these negative materials that embodiment 24-31 provides have good cycle performance.
Embodiment 32-41
Embodiment 32-41 provides a kind of preparation method of the negative pole for lithium ion battery respectively, these preparation methods are substantially identical with the method in embodiment 1, and their difference is only carbon nano-tube to be replaced with respectively porous carbon (embodiment 32), carbon fiber (embodiment 33), conductive black (embodiment 34), graphite (embodiment 35), petroleum coke (embodiment 36), polypyrrole fiber (embodiment 37), polyaniline fiber (embodiment 38), polythiophene fiber (embodiment 39), copper powder (embodiment 40), copper fiber (embodiment 41).
In order to further illustrate the performance of the composite negative pole material that embodiment 32-41 provides, the negative pole containing this composite negative pole material utilizing the method identical with embodiment 6 to be provided by embodiment 32-41 makes battery respectively.Carry out charge-discharge test to these batteries, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that these negative materials that embodiment 32-41 provides have good cycle performance.
Embodiment 42
The present embodiment provides a kind of lithium ion battery, and it is substantially identical with the lithium ion battery provided in embodiment 1, and its difference is electrolyte to replace with PEO-LiTFSI polymer dielectric.Wherein the mol ratio of EO and Li is 16:1.
In 70 DEG C of air dry ovens, carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of this battery, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the lithium ion battery that the present embodiment provides has good cycle performance.
Embodiment 43-50
Embodiment 43-50 provides a kind of lithium ion battery respectively, and it is substantially identical with the lithium ion battery provided in embodiment 24-31, and its difference is the electrolyte of the lithium ion battery provided in embodiment 24-31 to replace with PEO-LiTFSI polymer dielectric respectively.Wherein the mol ratio of EO and Li is 20:1.
In 70 DEG C of air dry ovens, carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the lithium ion battery that embodiment 43-50 provides has good cycle performance.
Embodiment 51-59
Embodiment 51-59 provides a kind of lithium ion battery respectively, it is substantially identical with the lithium ion battery provided in embodiment 1,24-31, and its difference is the electrolyte of the lithium ion battery provided in embodiment 1,24-31 to replace with PEO-LiTFSI/10wt.%SiO respectively 2polymer dielectric.Wherein the mol ratio of EO and Li is 16:1, Nano-meter SiO_2 2be 10% relative to the mass ratio of PEO and LiTFSI.
In 70 DEG C of air dry ovens, carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the lithium ion battery that embodiment 51-59 provides has good cycle performance.
Embodiment 60-63
Embodiment 60-63 provides a kind of lithium ion battery respectively, and it is substantially identical with the lithium ion battery provided in embodiment 51, and its difference is the PEO-LiTFSI/10wt.%SiO in the lithium ion battery that provides in embodiment 51 2siO in polymer dielectric 2replace with Al respectively 2o 3, MgO, ZrO 2, Li 3pO 4-xn x.
In 70 DEG C of air dry ovens, carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the lithium ion battery that embodiment 60-63 provides has good cycle performance.
Embodiment 64-67
Embodiment 64-67 provides a kind of lithium ion battery respectively, and it is substantially identical with the lithium ion battery provided in embodiment 52, and its difference is the PEO-LiTFSI/10wt.%SiO in the lithium ion battery that provides in embodiment 52 2siO in polymer dielectric 2replace with Al respectively 2o 3, MgO, ZrO 2, Li 3pO 4-xn x.
In 70 DEG C of air dry ovens, carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the lithium ion battery that embodiment 64-67 provides has good cycle performance.
Embodiment 68-71
Embodiment 68-71 provides a kind of lithium ion battery respectively, and it is substantially identical with the lithium ion battery provided in embodiment 59, and its difference is the PEO-LiTFSI/10wt.%SiO in the lithium ion battery that provides in embodiment 59 2siO in polymer dielectric 2replace with Al respectively 2o 3, MgO, ZrO 2, Li 3pO 4-xn x.
In 70 DEG C of air dry ovens, carry out charge-discharge test to this battery, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that the lithium ion battery that embodiment 68-71 provides has good cycle performance.
Embodiment 72-76
Embodiment 72-76 provides a kind of preparation method of the negative pole for lithium ion battery respectively, and these preparation methods are substantially identical with the method in embodiment 1, and their difference is only nano silica fume to replace with nanometer glass putty, SnO respectively 2, SnCo, SiO, FeSi.
In order to further illustrate the performance of the composite negative pole material that embodiment 72-76 provides, the negative pole containing this composite negative pole material utilizing the method identical with embodiment 1 to be provided by embodiment 72-76 makes battery respectively.Carry out charge-discharge test to these batteries, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that these negative materials that embodiment 72-76 provides have good cycle performance.
Embodiment 77-81
Embodiment 77-81 provides a kind of preparation method of the negative pole for lithium ion battery respectively, these preparation methods are substantially identical with the method in embodiment 42, and their difference is only nano silica fume to replace with nanometer glass putty, SnO2, SnCo, SiO, FeSi respectively.
In order to further illustrate the performance of the composite negative pole material that embodiment 77-81 provides, the negative pole containing this composite negative pole material utilizing the method identical with embodiment 1 to be provided by embodiment 77-81 makes battery respectively.Carry out charge-discharge test to these batteries, voltage range is 0.005-1.5V, and test result is as shown in table 1.As can be seen from Table 1, the level of the head week charge specific capacity of these batteries, first all specific discharge capacities, first all coulombic efficiency and 50 weeks rear capability retentions is all very good, shows that these negative materials that embodiment 77-81 provides have good cycle performance.
The electrochemistry circulation of above-described embodiment the results are shown in Table 1:
Table 1 (charging and discharging capacity=charge/discharge capacity/combination electrode material quality)
In lithium ion battery, there is redox reaction by electronics-lithium ion at the Charger transfer of its near surface thus realize conversion and the storage of energy in the negative active core-shell material in negative pole.The invention provides a kind of composite negative pole material, by the Surface coating electrons/ions mixed conductor material at negative active core-shell material, this electrons/ions mixed conductor material is separated with between making in negative active core-shell material between each particle, both can prevent the efflorescence of negative active core-shell material, the rapid electric charge transfer of the electronics-lithium ion on negative active core-shell material surface can have been ensured again.
It should be noted that, said in the present invention " electrons/ions mixed conductor material " refers to that room temperature (25 DEG C) electronic conductivity and conductivity at room temperature are all greater than 10 -20s cm -1electric conducting material.
According to other embodiments of the invention, wherein electrons/ions mixed conductor material refers to the material simultaneously with ion and electron conduction ability.It can be single structure compound or pure metals, also can be the mixture comprising multiple compounds or simple substance.Simple substance in mixture such as can be selected from B, C, P, S, Mg, Al, Si, Ca, Sc, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Se, Ba, Ge, Sr, Y, Zr, Sn, Sb, Pb, Ba, Mo, W.Mixture can also alloy containing one of these elements or compound and combination thereof.
According to other embodiments of the invention, wherein electrons/ions mixed conductor material can be the mixture of macromolecular material, lithium salts and electronic conductive material.Wherein macromolecular material can be such as polypyrrole (PPy), polyaniline (PANi), polythiophene (PTh), PEDOT, phthalocyanines, polyacrylonitrile (PAN), Pluronic F-127 (PEO), polyethylene (PE), polypropylene (PP), polymethyl methacrylate (PMMA), Kynoar (PVDF), polyvinyl chloride (PVC), polyimides (PI), polyamidoimide (PAI), polyamide (PA), polyacrylic acid (PAA) etc.Lithium salts can be such as LiClO 4, LiPF 6, LiBF 4, LiTFSI, LiFSI, LiBOB, Li 3pO 4-xn xdeng.Electronic conductive material can be such as various material with carbon element (carbon nanocoils, carbon nano-tube, carbon nano-fiber, carbon black, graphite, RESEARCH OF PYROCARBON, petroleum coke, porous carbon etc.), metallic fiber or metal powder (as Cu, Ti, Fe, Mg, Sn) etc.Namely some macromolecular material itself has electron conduction, if polypyrrole (PPy), polyaniline (PANi), polythiophene (PTh), PEDOT, phthalocyanines etc. are containing heteroatomic conjugated polymer etc.For this macromolecular material with electron conduction, it can be formed after mixing with lithium salts according to electrons/ions mixed conductor material of the present invention, without the need to additionally adding electronic conductive material, or only need add a small amount of electronic conductive material.
According to other embodiments of the invention, wherein nano-ceramic particle can also be had, as SiO in electrons/ions mixed conductor material 2, Al 2o 3, MgO, ZrO 2, Li 3pO 4-xn xdeng.Nano-ceramic particle add the conduction that can strengthen lithium ion.
According to other embodiments of the invention, wherein electrons/ions mixed conductor material can be other the material not only having electron conduction but also have ionic conductivity.Those skilled in the art can select suitable material according to actual needs and neatly.
In above-described embodiment, for silica-based and tin base cathode active material, describe according to technical scheme of the present invention.According to other embodiments of the invention, electrons/ions mixed conductor material provided by the invention also may be used for other negative active core-shell material coated.
The method provided in above-described embodiment is provided according to the preparation method of the electrons/ions mixed conductor material provided of the present invention.Those skilled in the art can select other preparation method neatly according to actual needs.
According in the electrons/ions mixed conductor material provided of the present invention, proportioning between each component is not limited to the ratio provided in above-described embodiment, and those skilled in the art easily can select the proportioning of wherein each component according to selected electrons/ions mixed conductor material.But usually, in electrons/ions mixed conductor material, preferably, the mol ratio of macromolecular material and lithium salts is between 2:1 ~ 40:1, preferably, nano ceramics relative to the mass ratio of macromolecular material and lithium salts sum between 50% ~ 0%, preferably, electronic conductive material relative to the mass ratio of macromolecular material and lithium salts sum between 500% ~ 0%.
According in the composite negative pole material provided of the present invention, the ratio of electrons/ions mixed conductor material and negative active core-shell material is also not limited to the ratio provided in above-described embodiment, and those skilled in the art easily can select the proportioning of wherein each component according to selected electrons/ions mixed conductor material and negative active core-shell material.Usually, the ratio of electrons/ions mixed conductor material and negative active core-shell material is preferably 9 ~ 0.02.
It should be noted last that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, modify to technical scheme of the present invention or equivalent replacement, do not depart from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.

Claims (9)

1. for a composite negative pole material for lithium ion battery, comprise negative active core-shell material and electrons/ions mixed conductor material, wherein said negative active core-shell material is covered by described electrons/ions mixed conductor material.
2. composite negative pole material according to claim 1, wherein said electrons/ions mixed conductor material is all greater than 10 at the electronic conductivity of 25 DEG C and ionic conductivity -20s cm -1.
3. composite negative pole material according to claim 1, wherein said electrons/ions mixed conductor material is mixture, comprises electronic conductive material and ion conductive material.
4. composite negative pole material according to claim 3, described electronic conductive material be selected from carbon, metal, conducting polymer composite one or more.
5. composite negative pole material according to claim 3, described ion conductive material is mixture, comprises macromolecular material and lithium salts.
6. composite negative pole material according to claim 1, wherein said electrons/ions mixed conductor material comprises conducting polymer composite and lithium salts.
7. the composite negative pole material according to claim 3 or 6, wherein said electrons/ions mixed conductor material also comprises nano-ceramic particle.
8. composite negative pole material according to claim 1, wherein said negative active core-shell material is silicon, tin, SnO 2, SnCo, SiO or FeSi.
9. a lithium ion battery, comprises the composite negative pole material according to any one of claim 1-8.
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Application publication date: 20150513