CN109103441A - Modified composite material, preparation method and the purposes in lithium ion battery of siliceous substrates material - Google Patents
Modified composite material, preparation method and the purposes in lithium ion battery of siliceous substrates material Download PDFInfo
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- CN109103441A CN109103441A CN201811049206.8A CN201811049206A CN109103441A CN 109103441 A CN109103441 A CN 109103441A CN 201811049206 A CN201811049206 A CN 201811049206A CN 109103441 A CN109103441 A CN 109103441A
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 239000000758 substrate Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 97
- 238000000034 method Methods 0.000 claims abstract description 65
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 9
- 229920005596 polymer binder Polymers 0.000 claims description 19
- 239000002491 polymer binding agent Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000007773 negative electrode material Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 15
- 238000002604 ultrasonography Methods 0.000 claims description 13
- 238000005253 cladding Methods 0.000 claims description 12
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000661 sodium alginate Substances 0.000 claims description 11
- 235000010413 sodium alginate Nutrition 0.000 claims description 11
- 229940005550 sodium alginate Drugs 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 9
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 9
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 229920001940 conductive polymer Polymers 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 2
- 150000004702 methyl esters Chemical class 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 30
- 239000010405 anode material Substances 0.000 abstract description 6
- 238000010410 dusting Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000005562 fading Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 102220043159 rs587780996 Human genes 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910020381 SiO1.5 Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of modified composite material of siliceous substrates material, preparation method and in the purposes of lithium ion battery, the composite material includes silicon substrate kernel, and is coated on the polymer covering layer of the core surface.The described method includes: 1) polymer is added in liquid solvent, dispersion obtains slurry；2) mixture of silica-base material or silica-base material and carbon material is added in slurry, solid-liquid mixing；3) solvent is removed, the modified composite material of siliceous substrates material is obtained.On the one hand the present invention can isolate electrolyte, hinder electrolyte in the side reaction on its surface by introducing polymer covering layer in silicon substrate core surface；On the other hand, situations such as crushing, electrode dusting and peeling of the silicon based anode material in processing and use process can also be improved, silica-base material is reduced in charge and discharge process because electrode caused by huge volume expansion crushes, removes situation, reach stable electrode structure, improves the purpose of battery core cycle performance.
Description
Technical field
The invention belongs to technical field of lithium ion, are related to modified composite material, its preparation of a kind of siliceous substrates material
Method and purposes in lithium ion battery.
Background technique
Since lithium ion battery has high-energy density, high voltage and the properties such as environmental-friendly, it is widely used in just
It takes on formula power equipment (such as mobile phone, computer) and electric car.But due to by battery material, conductive additive and
The influence of binder etc., being difficult preparation at present has high reversible capacity, the lithium-ion electric of high circulation stability and high rate capability
Pond.
Negative electrode material is the extremely important component part of lithium ion battery, and the energy for directly influencing lithium ion battery is close
Degree and chemical property.The reversible capacity, cycle performance, high rate performance of lithium ion battery can be improved in excellent negative electrode material；
Otherwise it will cause the decaying of lithium ion performance, or even can not work.
Traditional graphite cathode material theoretical specific capacity is 372mAh/g, practical application material capacity is reachable > 360mAh/g,
Almost without room for improvement；In contrast, silicon has high specific discharge capacity (4200mAh/g), it is graphite negative electrodes material
10 times or more.The theoretical capacity of SiO is also in 1400mAh or more.Use high performance silica-base material as negative electrode active material
One of most promising route of battery energy density is improved as current.But silicon based electrode can be brought in charge and discharge process it is huge
Big volume expansion, causes dusting to be peeled off, and makes to lose electrical contact between active material and between its collector；In addition dusting
New SEI film is constantly formed in the process, further results in the lower cycle life of battery.
Carbon-coating cladding is paid close attention to the surface coating modification early stage of silica-base material, to improve the electrical conductance and mechanicalness of material
Energy.For example it includes: carbon pipe that CN 104112847A, which discloses a kind of silicon based anode material and its method, the silicon based anode material,
Silicon particle can be made to be fixed in carbon pipe since there is gap inside carbon pipe with the silicon nanoparticle being located inside the carbon pipe
In limited space, so that the volume expansion or contraction of silicon particle not only avoid influence activity in the limited space
Electronic transmission performance between material and collector, and the thickening phenomenon of SEI film is avoided, it is conducive to improve lithium battery capacity and property
Energy performance, however carbon pipe lacks ductility, and the tension of volume expansion generation can not be effectively absorbed in electrode charge and discharge process,
So the dusting of particle can not be prevented to delay.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of modifications of siliceous substrates material
Composite material, preparation method and the purposes in lithium ion battery.The present invention contains Si/SiO by using lithium ion batteryxCathode
Material carries out polymer surfaces coating modification to improve its chemical property, including the reversible appearance in battery use process
Amount, first charge discharge efficiency and cycle life.
In order to achieve the above object, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of modified composite material of siliceous substrates material, the composite material includes silicon substrate
Kernel, and it is coated on the polymer covering layer of the core surface.
Polymer covering layer of the present invention is the high molecular polymer clad with caking property, the polymer covering layer
Compact structure contains reactive group in preferred polymers clad.
On the one hand the present invention can isolate electrolyte, hinder electricity by introducing polymer covering layer in silicon substrate core surface
Liquid is solved in the side reaction on its surface, improves the overall performance of battery；On the other hand, modified composite material of the invention also solves
Silicon based anode material needs the problem of special protection when in use, since polymer has caking property and ductility, can lead to
It crosses deformation and absorbs tension, so as to improve silicon based anode material in processing and crushing, electrode dusting and the stripping in use process
Situations such as falling, reduction silica-base material (such as Si and/or SiOxNegative electrode material) it is swollen because of huge volume in charge and discharge process
Electrode caused by swollen crushes, removes situation, still is able to maintain the complete of material granule to a certain extent after Particle Breakage,
Reach stable electrode structure, improves the purpose of battery core cycle performance.
As the optimal technical scheme of modified composite material of the present invention, the gross mass with the composite material is
100wt% meter, the mass percentage of the polymer covering layer are 0.5wt%~10wt%, such as 0.5wt%, 1wt%,
2wt%, 2.5wt%, 3.5wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt% etc., preferably
1wt%~5wt%.
Preferably, the group of the polymer covering layer become Kynoar PVDF and its improve product, high polymer binder,
In electronic conductance polymer or ionic conductance polymer any one or at least two combination.
Preferably, the high polymer binder is sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) or sodium alginate
In any one or at least two combination.
Preferably, the electronic conductance polymer is any one in polyaniline, polythiophene or polypyrrole or at least two
The combination of kind.
Preferably, the ionic conductance polymer is polyacrylic acid (PAA), polyacrylamide (PAM), polyvinyl alcohol resin
In fiber (PAV) or polymethyl methacrylate (PMMA) any one or at least two combination.
It is highly preferred that polymerizeing in the composition of the polymer covering layer comprising electronic conductance polymer and/or ionic conductance
Object.
" including electronic conductance polymer and/or ionic conductance polymer " of the present invention refers to: can be only comprising electronics electricity
Polymer is led, can also only include ionic conductance polymer, can also not only comprising electronic conductance polymer but also include ionic conductance
Polymer.
Since most of high molecular polymers have electrochemicaUy inert, lithium ion can be hindered in the insertion of surface of active material
With abjection, which becomes apparent in high magnification, can significantly affect the high rate performance of lithium-ion-power cell.This is preferably
In technical solution, coat by introducing electronic conductance polymer and can improve electric conductivity while keeping structural stability
Can, the composite material made has both good caking property and electric conductivity；Carrying out cladding by introducing ionic conductance polymer can
To improve lithium ionic mobility while keeping structural stability, the composite material made have both good caking property and from
Sub- migration performance；It carries out cladding by introducing electronic conductance polymer and ionic conductance polymer simultaneously and structure can kept steady
Electric conductivity and Ion transfer performance are improved while qualitative.
As the optimal technical scheme of modified composite material of the present invention, the group of the polymer covering layer becomes high score
Sub- binder, above-mentioned binder are the common binders of lithium ion battery, using these high polymer binders to silicon substrate kernel into
Row cladding, not only can use the mechanical strength and ductility of polymer material, produce in silica-base material insertion/deintercalate lithium ions
The tension generated in absorption process when raw volume change reduces fresh surfaces to be conducive to the holding of material granule pattern
It generates；The negative electrode material that will be obtained can also be improved and conventional binder (such as sodium carboxymethylcellulose or butadiene-styrene rubber) is mixed
Conjunction prepares processing performance when cathode, and above-mentioned factor collective effect improves the stability and dynamic performance of silica-base material, by it
Applied to lithium ion battery, cycle performance, high rate performance, the capacity performance of product and the first effect of battery are greatly improved.
The preferably combination of sodium carboxymethylcellulose and butadiene-styrene rubber.
It is highly preferred that the composition of the polymer covering layer are as follows: in mass ratio by sodium carboxymethylcellulose and butadiene-styrene rubber
The combination of 1:99~99:1, the mass ratio such as 1:99,5:95,10:90,20:80,25:75,30:70,40:60,50:50,
60:40,70:30,80:20,90:10 or 99:1 etc..Can be obtained using the combination of both substances preferably improves cyclicity
Energy, high rate performance and product capacity play and the effect of first effect, and specific ratio depends on silica-base material surface to the affine of solvent
Power, those skilled in the art can optimize the cladding process of material therefor by both regulations ratio.
As the another optimal technical scheme of modified composite material of the present invention, the group of the polymer covering layer becomes
The combination of high polymer binder and ionic conductive polymer, the aforementioned high polymer binder cladding process the advantages of other than, ion
The addition of conducting polymer is conducive to improve lithium ion conduction rate of the lithium ion at solid-electrolyte interface, improves cathode
The dynamic performance of material in the application, which improves the stability and dynamic performance of silica-base material, by it
Applied to lithium ion battery, can reduce the polarization phenomena of battery, the cycle performance of battery, high rate performance, product capacity hair
It waves and first effect is greatly improved.The preferably combination of sodium alginate and polyacrylic acid, further preferably sodium alginate and
The polyacrylic acid combination of 1:4~4:1 in mass ratio.The mass ratio for example 1:4,1:3,1:2,1:2,2:1,3:1 or 4:1
Deng.
As the optimal technical scheme of modified composite material of the present invention, the polymer covering layer with a thickness of 5nm
~50nm, such as 5nm, 8nm, 10nm, 12nm, 15nm, 20nm, 25nm, 30nm, 32nm, 36nm, 40nm, 45nm or 50nm etc.,
If thickness is less than 5nm, excessively thin clad has difficulties in actually preparation, it is possible to lead to the incomplete and uneven of cladding
It is even, to lose the effect of cladding；If thickness is greater than 50nm, blocked up clad will affect negative electrode material in use
Mass transfer reduces the dynamic performance of material while increasing interface impedance.
Preferably, the partial size of the silicon substrate kernel is at 1 μm~20 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 4.5 μm, 5 μm, 6 μ
M, 8 μm, 10 μm, 12 μm, 14 μm, 15 μm, 17 μm, 18 μm or 20 μm etc..
Preferably, the composition of the silicon substrate kernel are as follows: the combination of silica-base material or silica-base material and carbon material, it is described
Silica-base material preferably includes Si or SiOxIn any one or two kinds of arbitrary proportions combination, 0 < x < 2, the carbon material is preferred
Combination including any one or two kinds in artificial graphite or natural graphite.The combination of the silica-base material and carbon material can be with
It is the Si or SiO of carbon-coating packagexMaterial etc., but it is not limited to the combination of silica-base material and carbon material, it can also be that other are siliceous
The negative electrode material of sill.
Second aspect, the present invention provide the preparation side of the modified composite material of siliceous substrates material as described in relation to the first aspect
Method the described method comprises the following steps:
(1) polymer is added in liquid solvent, dispersion obtains slurry；
(2) mixture of silica-base material or silica-base material and carbon material is added in slurry obtained by step (1), Gu
Liquid mixing；
(3) solvent is removed, the surface for making high molecular polymer be dispersed in silicon substrate kernel forms clad, obtains siliceous substrates
The modified composite material of material.
As the optimal technical scheme of the method for the invention, step (1) polymer be Kynoar PVDF and
Its improve product, high polymer binder, in electronic conductance polymer or ionic conductance polymer any one or at least two
Combination.
Preferably, the high polymer binder is any one in sodium carboxymethylcellulose, butadiene-styrene rubber or sodium alginate
Kind or at least two combination.
Preferably, the electronic conductance polymer is any one in polyaniline, polythiophene or polypyrrole or at least two
The combination of kind.
Preferably, the ionic conductance polymer is polyacrylic acid, polyacrylamide, polyvinyl alcohol resin fiber or poly- first
In base methyl acrylate any one or at least two combination.
Preferably, when the polymer is high polymer binder or high polymer binder and ionic conductive polymer
When combination, the liquid solvent includes water, N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) or N, N- dimethyl formyl
In amine (DMF) any one or at least two combination, above-mentioned solvent is suitable for existing battery process, it is not necessary to additional new
Equipment investment；Disperse the obtained solid content of slurry 20%~95%, such as 20%, 25%, 30%, 35%, 40%,
45%, 50%, 60%, 65%, 70%, 75%, 80%, 90% or 95% etc., good cladding can be taken into account within this range
Uniformity and preparation low energy consumption, and it is solid better containing the lower degree that is evenly coated, Gu it is lower containing more high then process energy consumption.
As the optimal technical scheme of the method for the invention, step (1) described dispersion are as follows: by stirring, vibration or surpass
Sound is realized evenly dispersed.
Preferably, step (2) the solid-liquid mixing are as follows: uniformly mixing is realized by stirring, vibration or ultrasound.
Preferably, the method for step (3) the removal solvent includes: any one in filtering, evaporation or spray drying
Or at least two combination.
Preferably, the method also includes carrying out step (4) after removing solvent: heat treatment, can be with by heat treatment
The crosslinking degree for improving clad makes it be unlikely in following process, use process dissolution dispersion again.
Preferably, the temperature of the heat treatment is 100 DEG C~250 DEG C, such as 100 DEG C, 120 DEG C, 150 DEG C, 165 DEG C, 185
DEG C, 200 DEG C, 210 DEG C, 225 DEG C, 235 DEG C or 250 DEG C etc., if temperature is lower than 100 DEG C, the solvent that the too low part of temperature combines
It not can be removed, fine and close clad structure can not be formed by reactions such as condensations between polymer, thus in next slurry system
Dissolution/dispersion in standby process and battery use process, cannot keep the form of clad；If temperature is higher than 250 DEG C, temperature mistake
Height may cause the disengaging of reactive group and the destruction of polymer architecture, function, finally be unable to reach herein described technique
Effect.
Preferably, the time of the heat treatment be greater than 1h, such as 1.5h, 2h, 3h, 4h, 5h, 6h, 8h, 10h, 12h, 15h,
After 18h, 20h for 24 hours etc..
The third aspect, the present invention provide a kind of cathode, and the cathode includes that modified composite material described in first aspect is made
For negative electrode active material.
Fourth aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes to bear described in the third aspect
Pole.
Compared with the prior art, the invention has the following beneficial effects:
(1) present invention is by introducing the high molecular polymer clad with caking property in silicon substrate core surface, on the one hand
It can isolate electrolyte, hinder electrolyte in the side reaction on its surface, improve the overall performance of battery；On the other hand, due to poly-
Closing object has caking property and ductility, can absorb tension by deformation, add so as to improve silicon based anode material
Crushing, electrode dusting in work and use process and situations such as peel off reduce silica-base material (such as Si and/or SiOx cathode material
Material) it is crushed in charge and discharge process because of electrode caused by huge volume expansion, situation is removed, thus stablize electrode structure,
Improve the cycle performance of battery core.
(2) by introducing electronic conductance polymer and/or ionic conductance polymer in polymer covering layer, can
It keeps improving electric conductivity and/or Ion transfer performance while structural stability, improves it applied to lithium-ion-power cell
When chemical property, especially high rate performance.
(3) become common high polymer binder by limiting the group of polymer covering layer, silica-base material can be improved
Stability and dynamic performance, are applied to lithium ion battery, the cycle performance of battery, high rate performance, product capacity hair
It waves and first effect is greatly improved.
(4) become the combination of high polymer binder and ionic conductive polymer by limiting the group of polymer covering layer, it can
To improve the stability and dynamic performance of silica-base material, it is applied to lithium ion battery, the polarization that can reduce battery is existing
As cycle performance, energy density, high rate performance, the capacity performance of product and the first effect of battery are greatly improved.
Detailed description of the invention
Fig. 1 be using the siliceous substrates material of embodiment 1-5 modified composite material and comparative example 1 without clad
The Capacity fading curve graph of soft-package battery made of SiO.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
The present embodiment provides a kind of modified composite material of siliceous substrates material, the composite materials are as follows: SiO kernel, and packet
The polymer covering layer of the core surface is overlayed on, the group of the polymer covering layer becomes Kynoar；
D50=5 μm of partial size of the SiO kernel, the Kynoar clad with a thickness of 10nm；
By the gross mass of modified composite material for 100wt% in terms of, the mass percentage of the Kynoar clad
For 3wt%.
Preparation method:
(1) it disperses polymer in NMP liquid solvent, it is evenly dispersed by the methods of stirring, vibration, ultrasound, it obtains
To slurry；
(2) SiO negative materials are added in slurry, realize that solid-liquid uniformly mixes by the methods of stirring, vibration, ultrasound
It closes；
(3) using the methods of filtering, evaporation removal solvent, high molecular polymer is made to be dispersed in surface containing SiO negative materials
Form clad；
(4) crosslinking degree that clad is improved by heat treatment, is not it in following process, use process again
Dissolution dispersion, heat treatment temperature are 150 DEG C, and the time is for 24 hours, to finally obtain modified composite material.
Using:
Negative electrode active material is used as according to the ratio mixing of 1:9 using the modified composite material and artificial graphite of the present embodiment
Matter is made cathode and is further assembled into lithium ion battery, reaches the effect for improving lithium ion high-energy density and long circulating performance
Fruit.Its energy density be 230Wh/kg, Capacity fading curve see Fig. 1 (loop test condition are as follows: under the conditions of 25 DEG C, 0.5C
The 1C that charges discharges).
The present embodiment prepares the specific steps of lithium ion battery are as follows: disperses positive electrode, conductive agent, positive electrode binder in
In NMP and stirring forms anode sizing agent, is coated on aluminium foil and obtains anode pole piece by drying, roll-in, cutting；By cathode material
Material, conductive agent, negative electrode binder are dispersed in water and stir to form negative electrode slurry, be coated on copper foil and by drying, roll-in,
Cutting obtains cathode pole piece.Above-mentioned positive and negative electrode pole piece is wound together with isolation film, injects electrolyte after outsourcing aluminum plastic film
And it is sealed.Test soft bag lithium ionic cell is finally obtained after the processes such as standing, chemical conversion, partial volume.
Embodiment 2
The present embodiment provides a kind of modified composite material of siliceous substrates material, the composite materials are as follows: SiO1.5Kernel, and
It is coated on the polymer covering layer of the core surface, the composition of the polymer covering layer are as follows: CMC, SBR and polyaniline press matter
Measure the combination than 1:4:5；
D50=5 μm of partial size~10 μm of the SiO kernel, the polymer covering layer with a thickness of 10nm~25nm；
By the gross mass of modified composite material for 100wt% in terms of, the mass percentage of the polymer covering layer is
3wt%.
Preparation method:
(1) evenly dispersed by the methods of stirring, vibration, ultrasound by CMC, SBR and dispersing polyaniline in water, it obtains
Slurry；
(2) by SiO1.5Negative electrode material is added in slurry, realizes that solid-liquid uniformly mixes by the methods of stirring, vibration, ultrasound
It closes；
(3) using the methods of filtering, evaporation removal solvent, it is dispersed in high molecular polymer containing SiO1.5Negative electrode material table
Face forms clad；
(4) crosslinking degree that clad is improved by heat treatment, is not it in following process, use process again
Dissolution dispersion, heat treatment temperature are 200 DEG C, and time 3h finally obtains modified composite material.
Using:
Negative electrode active material is used as according to the ratio mixing of 1:9 using the modified composite material and artificial graphite of the present embodiment
Matter is fabricated in the same manner as in Example 1 cathode and is further assembled into lithium ion battery, reaches and improves lithium ion high energy
The effect of metric density and long circulating performance.Its energy density is 230Wh/kg, and Capacity fading curve is shown in Fig. 1 (loop test
Condition is same as Example 1).
Embodiment 3
The present embodiment provides a kind of modified composite material of siliceous substrates material, the composite materials are as follows: SiO kernel, and packet
Overlay on the polymer covering layer of the core surface, the composition of the polymer covering layer are as follows: CMC, SBR, sodium alginate and PAA
By the combination of 1:4:1:1；
D50=10 μm of partial size~15 μm of the SiO kernel, the polymer covering layer with a thickness of 30nm~50nm；
By the gross mass of modified composite material for 100wt% in terms of, the mass percentage of the polymer covering layer is
5wt%.
Preparation method:
(1) CMC, SBR, sodium alginate and PAA are dispersed in water, are uniformly divided by the methods of stirring, vibration, ultrasound
It dissipates, obtains slurry；
(2) SiO negative materials are added in slurry, realize that solid-liquid uniformly mixes by the methods of stirring, vibration, ultrasound
It closes；
(3) using the methods of filtering, evaporation removal solvent, high molecular polymer is made to be dispersed in surface containing SiO negative materials
Form clad；
(4) crosslinking degree that clad is improved by heat treatment, is not it in following process, use process again
Dissolution dispersion, heat treatment temperature are 125 DEG C, and time 12h finally obtains modified composite material.
Using:
Negative electrode active material is used as according to the ratio mixing of 1:9 using the modified composite material and artificial graphite of the present embodiment
Matter is fabricated in the same manner as in Example 1 cathode and is further assembled into lithium ion battery, reaches and improves lithium ion high energy
The effect of metric density and long circulating performance.Its energy density is 230Wh/kg, and Capacity fading curve is shown in Fig. 1 (loop test
Condition is same as Example 1).
Embodiment 4
The present embodiment provides a kind of modified composite material of siliceous substrates material, the composite materials are as follows: the SiO of carbon-coating cladding
Kernel, and be coated on the polymer covering layer of the core surface, the composition of the polymer covering layer are as follows: sodium alginate and poly-
The acrylic acid combination of 1:1 in mass ratio；
D50=1 μm of partial size~6 μm of the SiO kernel of carbon-coating cladding, the polymer covering layer with a thickness of 5nm
~20nm；
By the gross mass of modified composite material for 100wt% in terms of, the mass percentage of the polymer covering layer is
8wt%.
Preparation method:
(1) polymer is dispersed in water, it is evenly dispersed by the methods of stirring, vibration, ultrasound, obtain slurry；
(2) SiO negative materials are added in slurry, realize that solid-liquid uniformly mixes by the methods of stirring, vibration, ultrasound
It closes；
(3) using the methods of filtering, evaporation removal solvent, high molecular polymer is made to be dispersed in surface containing SiO negative materials
Form clad；
(4) crosslinking degree that clad is improved by heat treatment, is not it in following process, use process again
Dissolution dispersion, heat treatment temperature are 170 DEG C, and time 6h finally obtains modified composite material.
Using:
Negative electrode active material is used as according to the ratio mixing of 1:9 using the modified composite material and artificial graphite of the present embodiment
Matter is fabricated in the same manner as in Example 1 cathode and is further assembled into lithium ion battery, reaches and improves lithium ion high energy
The effect of metric density and long circulating performance.Its energy density is 230Wh/kg, and Capacity fading curve is shown in Fig. 1 (loop test
Condition is same as Example 1).
Embodiment 5
The present embodiment provides a kind of modified composite material of siliceous substrates material, the composite materials are as follows: SiO kernel, and packet
Overlay on the polymer covering layer of the core surface, the composition of the polymer covering layer are as follows: sodium carboxymethylcellulose and butylbenzene
The combination of press matter using rubbe amount ratio 40:60；
D50=3 μm of partial size~8 μm of the SiO kernel, the polymer covering layer with a thickness of 5nm~20nm；
By the gross mass of modified composite material for 100wt% in terms of, the mass percentage of the polymer covering layer is
7wt%.
Preparation method:
(1) it disperses polymer in NMP liquid solvent, it is evenly dispersed by the methods of stirring, vibration, ultrasound, it obtains
To slurry；
(2) SiO negative materials are added in slurry, realize that solid-liquid uniformly mixes by the methods of stirring, vibration, ultrasound
It closes；
(3) using the methods of filtering, evaporation removal solvent, high molecular polymer is made to be dispersed in surface containing SiO negative materials
Form clad；
(4) crosslinking degree that clad is improved by heat treatment, is not it in following process, use process again
Dissolution dispersion, heat treatment temperature are 215 DEG C, and time 3.5h finally obtains modified composite material.
Using:
Negative electrode active material is used as according to the ratio mixing of 1:9 using the modified composite material and artificial graphite of the present embodiment
Matter is fabricated in the same manner as in Example 1 cathode and is further assembled into lithium ion battery, reaches and improves lithium ion high energy
The effect of metric density and long circulating performance.Its energy density is 230Wh/kg, and Capacity fading curve is shown in Fig. 1 (loop test
Condition is same as Example 1).
Comparative example 1
This comparative example is the SiO without clad.
Using:
It is mixed using the SiO and artificial graphite of this comparative example according to the ratio of 1:9, using method same as Example 1
Cathode is made and is further assembled into lithium ion battery, measures its energy density and cycle performance.Its energy density is 230Wh/
Kg, Capacity fading curve are shown in Fig. 1 (loop test condition is same as Example 1).As shown in Figure 1, using of the invention
Lithium ion soft-package battery is made in the modified composite material of siliceous substrates material, and the cycle performance of battery can be substantially improved.
Battery obtained by various embodiments of the present invention not only has an excellent cycle performance, energy density also with higher, good
The capacity of good high rate performance, product plays and first effect is also greatly improved.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of modified composite material of siliceous substrates material, which is characterized in that the composite material includes silicon substrate kernel, and cladding
In the polymer covering layer of the core surface.
2. modified composite material according to claim 1, which is characterized in that the gross mass with the composite material is
100wt% meter, the mass percentage of the polymer covering layer are 0.5wt%~10wt%, preferably 1wt%~5wt%.
3. modified composite material according to claim 1 or 2, which is characterized in that the group of the polymer covering layer becomes
Kynoar PVDF and its improve product, high polymer binder, any in electronic conductance polymer or ionic conductance polymer
It is a kind of or at least two combination；
Preferably, the high polymer binder be sodium carboxymethylcellulose, butadiene-styrene rubber or sodium alginate in any one or
At least two combination；
Preferably, the electronic conductance polymer is any one in polyaniline, polythiophene or polypyrrole or at least two
Combination；
Preferably, the ionic conductance polymer is polyacrylic acid, polyacrylamide, polyvinyl alcohol resin fiber or poly- methyl-prop
In e pioic acid methyl ester any one or at least two combination；
It preferably, include electronic conductance polymer and/or ionic conductance polymer in the composition of the polymer covering layer.
4. modified composite material according to claim 1-3, which is characterized in that the group of the polymer covering layer
As high polymer binder, the preferably combination of sodium carboxymethylcellulose and butadiene-styrene rubber, further preferably carboxymethyl cellulose
Plain sodium and the butadiene-styrene rubber combination of 1:99~99:1 in mass ratio；
Preferably, the group of the polymer covering layer becomes the combination of high polymer binder and ionic conductive polymer, preferably
The combination of sodium alginate and polyacrylic acid, further preferably sodium alginate and the polyacrylic acid group of 1:4~4:1 in mass ratio
It closes.
5. modified composite material according to claim 1-4, which is characterized in that the thickness of the polymer covering layer
Degree is 5nm~50nm；
Preferably, the partial size of the silicon substrate kernel is at 1 μm~20 μm；
Preferably, the composition of the silicon substrate kernel are as follows: the combination of silica-base material or silica-base material and carbon material, the silicon substrate
Material preferably includes Si or SiOxIn any one or two kinds of arbitrary proportions combination, 0 < x < 2, the carbon material preferably includes
The combination of any one or two kinds in artificial graphite or natural graphite.
6. the preparation method of the modified composite material of siliceous substrates material as described in claim any one of 1-5, which is characterized in that institute
State method the following steps are included:
(1) polymer is added in liquid solvent, dispersion obtains slurry；
(2) mixture of silica-base material or silica-base material and carbon material is added in slurry obtained by step (1), solid-liquid is mixed
It closes；
(3) solvent is removed, the surface for making high molecular polymer be dispersed in silicon substrate kernel forms clad, obtains siliceous substrates material
Modified composite material.
7. according to the method described in claim 6, it is characterized in that, step (1) polymer be Kynoar PVDF and
Its improve product, high polymer binder, in electronic conductance polymer or ionic conductance polymer any one or at least two
Combination；
Preferably, the high polymer binder be sodium carboxymethylcellulose, butadiene-styrene rubber or sodium alginate in any one or
At least two combination；
Preferably, the electronic conductance polymer is any one in polyaniline, polythiophene or polypyrrole or at least two
Combination；
Preferably, the ionic conductance polymer is polyacrylic acid, polyacrylamide, polyvinyl alcohol resin fiber or poly- methyl-prop
In e pioic acid methyl ester any one or at least two combination；
Preferably, when the combination that the polymer is high polymer binder or high polymer binder and ionic conductive polymer
When, the liquid solvent include in water, N-Methyl pyrrolidone, dimethyl sulfoxide or n,N-Dimethylformamide any one or
At least two combination, the solid content of the slurry dispersed is 20%~95%.
8. method according to claim 6 or 7, which is characterized in that step (1) described dispersion are as follows: by stirring, vibration or
Ultrasound is realized evenly dispersed；
Preferably, step (2) the solid-liquid mixing are as follows: uniformly mixing is realized by stirring, vibration or ultrasound；
Preferably, step (3) it is described removal solvent method include: filtering, evaporation or spray drying in any one or extremely
Few two kinds of combination；
Preferably, the method also includes carrying out step (4) after removing solvent: heat treatment；
Preferably, the temperature of the heat treatment is 100 DEG C~250 DEG C；
Preferably, the time of the heat treatment is greater than 1h.
9. a kind of cathode, which is characterized in that the cathode includes the described in any item modified composite material conducts of claim 1-5
Negative electrode active material.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes cathode as claimed in claim 9.
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