CN106784747A - A kind of graphene-based lithium ion battery negative material - Google Patents
A kind of graphene-based lithium ion battery negative material Download PDFInfo
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- CN106784747A CN106784747A CN201710142248.5A CN201710142248A CN106784747A CN 106784747 A CN106784747 A CN 106784747A CN 201710142248 A CN201710142248 A CN 201710142248A CN 106784747 A CN106784747 A CN 106784747A
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- graphene
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- lithium ion
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000000463 material Substances 0.000 title claims abstract description 165
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 123
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 53
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 100
- 239000007772 electrode material Substances 0.000 claims abstract description 42
- 239000011148 porous material Substances 0.000 claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims description 58
- 239000005864 Sulphur Substances 0.000 claims description 51
- 239000007788 liquid Substances 0.000 claims description 46
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 238000006477 desulfuration reaction Methods 0.000 claims description 27
- 230000023556 desulfurization Effects 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 27
- 229910002804 graphite Inorganic materials 0.000 claims description 26
- 239000010439 graphite Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000017 hydrogel Substances 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- -1 graphite alkenes Chemical class 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000014121 butter Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000002956 ash Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052744 lithium Inorganic materials 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000011135 tin Substances 0.000 description 51
- 229910052718 tin Inorganic materials 0.000 description 50
- 229910052710 silicon Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 9
- 239000002388 carbon-based active material Substances 0.000 description 8
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000006245 Carbon black Super-P Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 235000001508 sulfur Nutrition 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to technical field of lithium ion, more particularly to a kind of graphene-based lithium ion battery negative material, negative material is three-dimensional porous Graphene non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon material being carried on three-dimensional porous Graphene, negative material has abundant pore structure, and its specific surface area is 170 400 m2/ g, pore volume is 0.18 1.2 cm3/ g, block density is 0.6 3.0 g/cm3, and the volume sum of negative material mesopore is 1.9 times 4 times of volume sum of non-carbon material.Relative to prior art, the negative material solves the problems, such as the volumetric expansion of non-carbon active component in the material, optimizes the density of composite, it is ensured that the ion transporting and electronic conductivity of composite.The material has the advantages that structure novelty, good conductivity, electrochemical lithium storage content be big, good cycle, while preparation method is simple, low cost is suitable to industrialization.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of graphene-based lithium with suitable headspace
Ion battery cathode material.
Background technology
Lithium ion battery is extensive since its commercialization due to having the advantages that energy density is high, good cycle
It is applied to portable electronic products, electric motor car and electrical network field.In particular with highlighting for energy and environment problem, lithium-ion electric
Pond has obtained increasing attention in the development of New Energy Industry.
The negative pole of lithium ion battery is the important component of battery, and its structure directly affects lithium ion battery with performance
Capacity, cycle performance and high rate performance.In current lithium ion battery negative material, realized extensive commercialization is graphite
Material.Graphite material low cost, wide material sources, are suitable to commercialization, but its specific discharge capacity is low, and Theoretical Mass specific capacity is only
372mAh/g；The density of graphite cathode is low simultaneously, and its theoretical volume specific capacity is only 800mAh/cm3, so limit lithium from
Development of the sub- battery in terms of high-quality specific capacity and high-volume and capacity ratio.
Non-carbon material such as silicon, metal oxide (such as SnO2、Fe2O3Deng) as lithium ion battery negative have matter very high
Amount specific capacity, and high density, so that with volume and capacity ratio very high.Wherein SnO2Specific capacity is up to 782mAh/g, but SnO2
As electrode material, Volume Changes are up to 260% in charge and discharge process, and this can cause the crushing of electrode, cause active material with
The open circuit of collector.Si bases negative material has the specific discharge capacity more than 3000mAh/g, but its volumetric expansion reaches 300%-
400%, the performance of its capacity is had a strong impact in charge and discharge process.Therefore, non-carbon material is because serious volumetric expansion problem
Limit its large-scale application in lithium ion battery negative.
Carbon material is introduced into for solving the problems, such as that volumetric expansion of the non-carbon negative material in cell operations is extremely closed
Key.Carbon skeleton to loading non-carbon active material is designed, and reserved suitable space meets non-carbon material in process of intercalation
Volumetric expansion, while design headspace, improve composite density, so as to prepare new carbon-non-carbon composite junction
Structure, specific discharge capacity and the volume and capacity ratio tool for improving lithium ion battery has very important significance.
Graphene as typical two-dimension flexible carbon material, with big specific surface and good electric conductivity.Graphene with
Non-carbon active material is combined, and is had a good application prospect in lithium ion battery material.Open Graphene skeleton structure, though
So can fully meet SnO2The volumetric expansion in process of intercalation, but the density of negative material is reduced, so as to limit its volume
The raising of performance.During three-dimensional grapheme water-setting glue is removed three-dimensional can be realized using the method for the capillary evaporation of water
The densification of graphene macroform.Non-carbon active material is carried in the three-dimensional grapheme macroscopic body of densification, can be significantly
Increase the density of composite, but excessively fine and close Graphene skeleton structure can not fully meet non-carbon active material embedding
Volumetric expansion during lithium, so as to have impact on the capability and performance of the composite, also results in the drop of negative material volume performance
It is low.
In view of this, it is necessory to provide a kind of graphene-based lithium ion battery negative material with suitable headspace
Material, its non-carbon active material that high density, high power capacity are loaded by designing Graphene skeleton introduces and optimizes headspace,
Meet the volumetric expansion of non-carbon active material, it is ensured that quick ion transmission channel and good electrical contact, improve quality
While specific capacity, highdensity lithium ion battery negative material is obtained, so as to realize the raising of volume performance.
The content of the invention
An object of the present invention is：In view of the shortcomings of the prior art, provide a kind of with suitable headspace
The preparation method of graphene-based lithium ion battery negative material, it loads high density, high power capacity by designing Graphene skeleton
Non-carbon active material, introduce and optimize headspace, meet the volumetric expansion of non-carbon active material, it is ensured that quick ion is passed
Defeated path and good electrical contact, while specific discharge capacity is improved, obtain highdensity lithium ion battery negative material,
So as to realize the raising of volume performance.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
A kind of graphene-based lithium ion battery negative material, the negative material is three-dimensional porous Graphene-non-carbon material
Combination electrode material, it includes three-dimensional porous Graphene and the non-carbon material being carried on the three-dimensional porous Graphene, described
Negative material has abundant pore structure, and its specific surface area is 170-400m2/ g, pore volume is 0.18-1.2cm3/ g, block density
It is 0.6-3.0g/cm3, and the volume sum of the negative material mesopore be 1.9 times of volume sum of the non-carbon material-
4 times.
Relative to prior art, the negative material solves the problems, such as the volumetric expansion of non-carbon active component in the material, excellent
The density of composite is changed, it is ensured that the ion transporting and electronic conductivity of composite.The material has structure novelty, leads
Electrically good, electrochemical lithium storage content is big, good cycle the advantages of, while preparation method is simple, low cost is suitable to industrialization.
When the three-dimensional porous Graphene-non-carbon material combination electrode material is as lithium ion battery negative material, its quality capacity can be with
500-2000mAh/g is reached, volume and capacity ratio can reach 500-3000mAh/cm3, and with excellent cycle performance and again
Rate performance.
Improved as one kind of graphene-based lithium ion battery negative material of the invention, the non-carbon material is titanium dioxide
At least one in tin, silicon and iron oxide.
Improved as one kind of graphene-based lithium ion battery negative material of the invention, it is three-dimensional many in the negative material
Hole Graphene is 1 with the mass ratio of non-carbon material:(1.6-4).Certain carbon component can alleviate the volumetric expansion of non-carbon material,
Increase the electric conductivity of material simultaneously；Because the finite capacity of carbon component, control carbon component is in relatively low content, it is possible to increase material
Overall specific discharge capacity, and density of material, and then realize volume and capacity ratio higher.
Improved as one kind of graphene-based lithium ion battery negative material of the invention, the preparation method of the negative material
At least comprise the following steps：
The first step, adds sulphur-containing substance and acid, acid fully to react generation sulphur with sulphur-containing substance in graphite alkenes dispersion liquid
Dispersion liquid in aqueous medium, and the presoma of non-carbon material is added, it is sufficiently stirred for obtaining mixed dispersion liquid；
Second step, the mixed dispersion liquid that the first step is obtained carries out hydro-thermal reaction in adding hydrothermal reaction kettle, obtains graphite
The compound hydrogel of alkene-non-carbon material-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, it is laggard
Row moisture removal, obtains pending product；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, and obtain three-dimensional porous Graphene-non-carbon materials
Material combination electrode material.With other oxide templates (SiO2Deng) compare, sulphur can be realized closely altogether with non-carbon active particle
Raw relation.After desulfurization, suitable expansion space can be reserved for non-carbon active particle.
The method by three-dimensional porous Graphene and non-carbon material composite construction introduce sulphur it is pre-filled as space
Template, after sulphur is removed, the space occupied by sulphur is volumetric expansion of the non-carbon material after embedding lithium and has reserved suitable sky
Between, so as to avoid the rupture of negative material and the efflorescence of electrode in charge and discharge process, improve the cyclicity of negative material
Can, finally realize excellent quality and volume performance.
The method has the following advantages that：
First, the method mild condition is simple to operate, preparation technology green non-pollution, is acted on using the capillary evaporation of water
The fine and close contraction of three-dimensional graphene framework can be realized, and using sulphur as the pre-filled template in space, it can removed
Afterwards, the space for being introduced into abundance meets volumetric expansion of the non-carbon material in charge and discharge process, prevent non-carbon material efflorescence and
Reunite, make electrode cycle performance be improved significantly.
Second, the method can realize Graphene skeleton to non-carbon material headspace in accuracy controlling interior on a large scale,
Specifically, the amount of the sulphur-containing substance by controlling to add, can regulate and control the size of headspace, with suitable for swollen with difference
The regulation and control of the headspace of the non-carbon material of swollen degree.
3rd, by content of the precise control sulphur in three-dimensional porous Graphene-non-carbon material combination electrode material, can be with
Suitable space is obtained, in the case where the requirement of non-carbon material volumetric expansion is met, it is to avoid too high porosity, obtained higher
Block density, so as in the case where excellent specific discharge capacity is realized, reach volume and capacity ratio high, resulting materials for
The raising tool of lithium ion battery quality and volume performance is of great significance.
Improved as one kind of graphene-based lithium ion battery negative material of the invention, in the first step, the dispersion of graphite alkenes
The mass ratio of the presoma of liquid, sulphur-containing substance, acid and non-carbon material is 1:(0.6-18):(0.25-1.5):(1-4.5), it is described
The concentration of graphite alkenes dispersion liquid is 1-3mg/mL.The quality proportioning of the precursor species has taken into full account each in prepared material
The content of component, can regulate and control each component content in suitable scope.
Improved as one kind of graphene-based lithium ion battery negative material of the invention, in the first step, described Graphene
Class dispersion liquid is at least one in graphene oxide dispersion, modified graphene dispersion liquid and porous graphene dispersion liquid；Institute
The sulphur-containing substance stated is at least one in distillation sulphur simple substance, sodium thiosulfate and vulcanized sodium；The acid is hydrochloric acid, nitric acid, sulphur
At least one in acid, sulfurous acid, carbonic acid and acetic acid；The presoma of described non-carbon material is butter of tin, stannous chloride, two
At least one in artificial gold, silica flour, ferric trichloride.
Improved as one kind of graphene-based lithium ion battery negative material of the invention, in second step, the temperature of hydro-thermal reaction
It is 100 DEG C -250 DEG C to spend, and hydro-thermal reaction duration is 3h-48h.At 100 DEG C -250 DEG C, sulphur has mobility and certain
Viscosity, by the hydro-thermal of 3h-48h, can either with non-carbon active particle realize sufficiently combine, while it can be avoided to roll into a ball
It is poly-.
Improved as one kind of graphene-based lithium ion battery negative material of the invention, in the 3rd step, the side of moisture removal
Method is drying, and drying temperature is 60 DEG C -90 DEG C, and baking duration is 6h-72h.In drying course, steamed using the capillary of water
Hair, realizes the contraction to material.60 DEG C -90 DEG C can realize that block preferably shrinks, while fast under the conditions of avoiding higher temperature
Speed is shunk the block for causing and is crushed；The drying time of 6h-72h can realize the abundant drying to material.
Improved as one kind of graphene-based lithium ion battery negative material of the invention, in the 4th step, desulfurization process are heat
Desulfurization is processed, the method for being heat-treated desulfurization is：Under inert gas shielding atmosphere, it is warming up to the heating rate of 3-20 DEG C/min
300 DEG C -500 DEG C, then constant temperature 3h-24h, sulphur is removed, and is cooled to room temperature.The fusing point and boiling point of sulphur are relatively low, heat treatment
Method can realize the thorough removing to sulphur.
Improved as one kind of graphene-based lithium ion battery negative material of the invention, in the 4th step, desulfurization process are molten
Agent method desulfurization.It is placed in carbon disulfide after pending product is ground, persistently stirs 6h-48h, fills the sulphur in pending product
Divide and be dissolved in carbon disulfide.Sulphur is soluble in carbon disulfide, and carbon disulfide desulfurization can equally realize the thorough removing to sulphur.
Brief description of the drawings
With reference to the accompanying drawings and detailed description, the present invention and its Advantageous Effects are described in detail.
Fig. 1 is the SEM figures of three-dimensional porous Graphene-tin ash macroscopic body material prepared by the embodiment of the present invention 1.
Fig. 2 is that the nitrogen adsorption of three-dimensional porous Graphene-tin ash macroscopic body material prepared by the embodiment of the present invention 1 takes off
Attached thermoisopleth (77K).
Fig. 3 is that the discharge and recharge of three-dimensional porous Graphene/tin ash macroscopic body material prepared by the embodiment of the present invention 1 is bent
Line.
Specific embodiment
Technical scheme, but protection scope of the present invention not limited to this are illustrated with specific embodiment below.
Embodiment 1
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 191m2/ g, pore volume is 0.25cm3/ g, block density is
2.18g/cm3, and the volume sum of negative material mesopore is 2.59 times of volume sum of non-carbon material.
Wherein, non-carbon material is tin ash, and three-dimensional porous Graphene is 1 with the mass ratio of tin ash:2.
The preparation method of the negative material is at least comprised the following steps：
The first step, takes 2mg/mL graphene oxide dispersions 78.5mL and is placed in 100mL beakers, adds 0.75g
Na2S2O3·5H2O, is subsequently adding 1M hydrochloric acid 6.5mL, and stirring 30min makes it fully react, is subsequently adding 350mg SnCl4·
5H2O, stirring makes it all dissolve, and obtains mixed dispersion liquid；
Second step, hydro-thermal reaction, water are carried out in the hydrothermal reaction kettle of the mixed dispersion liquid addition 100mL that the first step is obtained
Thermal response temperature is 150 DEG C, and the hydro-thermal duration is 6h, obtains the compound hydrogel of Graphene-tin ash-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, Zhi Hou
Sufficiently drying in 48h hours is carried out at 70 DEG C, by moisture removal, pending product is obtained；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, specifically, under argon gas protection, with
The heating rate of 10 DEG C/min is warming up to 400 DEG C, and then constant temperature 6 hours, sulphur is removed, and is cooled to room temperature, obtains three-dimensional porous
Graphene-tin ash combination electrode material.
The SEM of three-dimensional porous Graphene-tin ash macroscopic body material that embodiment 1 is provided is schemed as shown in figure 1, by Fig. 1
It can be seen that：The three-dimensional grapheme carbon skeleton result dense porous for tin ash active particle is provided, not only contributes to lithium
The transmission of ion and electronics, while volumetric expansion of the stannic oxide particle in process of intercalation can be buffered.
The nitrogen adsorption desorption isotherm of three-dimensional porous Graphene-tin ash macroscopic body material that embodiment 1 is provided
(77K) is as shown in Fig. 2 as seen from Figure 2：Three-dimensional porous Graphene has suitable pore structure and enough pore volume conducts
The headspace of tin ash.
Embodiment 1 provide three-dimensional porous Graphene/tin ash macroscopic body material charging and discharging curve as shown in figure 3,
As seen from Figure 3：Three-dimensional porous Graphene-tin ash macroscopic body material has first circle coulombic efficiency higher.
Embodiment 2
As different from Example 1：
The specific surface area of three-dimensional porous Graphene-tin ash combination electrode material is 256m2/ g, pore volume is 0.19cm3/
G, block density is 2.46g/cm3, and the volume sum of negative material mesopore is 1.98 times of volume sum of non-carbon material.
Wherein, non-carbon material is tin ash, and three-dimensional porous Graphene is 1 with the mass ratio of tin ash:2.
In the preparation method of the negative material, the consumption of graphene oxide dispersion is adjusted to 83.5mL, Na2S2O3·
5H2The consumption of O is adjusted to 0.10g, and hydrochloric acid consumption is adjusted to 1.5mL, and remaining is same as Example 1, repeats no more here.
Embodiment 3
As different from Example 1：
The specific surface area of three-dimensional porous Graphene-tin ash combination electrode material is 228m2/ g, pore volume is 0.21cm3/
G, block density is 2.32g/cm3, and the volume sum of negative material mesopore is 2.25 times of volume sum of non-carbon material.
Wherein, non-carbon material is tin ash, and three-dimensional porous Graphene is 1 with the mass ratio of tin ash:2.
In the preparation method of the negative material, the consumption of graphene oxide dispersion is adjusted to 82.5mL, Na2S2O3·
5H2The consumption of O is adjusted to 0.21g, and hydrochloric acid consumption is adjusted to 2.5mL.Remaining is same as Example 1, repeats no more here.
Embodiment 4
As different from Example 1：
The specific surface area of three-dimensional porous Graphene-tin ash combination electrode material is 182m2/ g, pore volume is 0.26cm3/
G, block density is 1.82g/cm3, and the volume sum of negative material mesopore is 2.72 times of volume sum of non-carbon material.
Wherein, non-carbon material is tin ash, and three-dimensional porous Graphene is 1 with the mass ratio of tin ash:2.
In the preparation method of the negative material, the consumption of graphene oxide dispersion is adjusted to 72mL, Na2S2O3·5H2O
Consumption be adjusted to 1.6g, hydrochloric acid consumption is adjusted to 13mL.Remaining is same as Example 1, repeats no more here.
Embodiment 5
As different from Example 1：
The specific surface area of three-dimensional porous Graphene-tin ash combination electrode material is 170m2/ g, pore volume is 0.27cm3/
G, block density is 1.10g/cm3, and the volume sum of negative material mesopore is 2.85 times of volume sum of non-carbon material.
Wherein, non-carbon material is tin ash, and three-dimensional porous Graphene is 1 with the mass ratio of tin ash:2.
In the preparation method of the negative material, the consumption of graphene oxide dispersion is adjusted to 55mL, Na2S2O3·5H2O
Consumption be adjusted to 3.4g, hydrochloric acid consumption is adjusted to 28mL.Remaining is same as Example 1, repeats no more here.
Comparative example 1
The specific surface area of three-dimensional porous Graphene-tin ash combination electrode material is 277m2/ g, pore volume is 0.18cm3/
G, block density is 2.65g/cm3, and the volume sum of negative material mesopore is 1.8 times of volume sum of non-carbon material.
In the preparation method of the negative material, Na2S2O3·5H2The consumption of O is adjusted to 0g, and hydrochloric acid consumption is adjusted to 0mL.
Remaining is same as Example 1, repeats no more here.
By the three-dimensional porous Graphene-tin ash combination electrode material prepared by embodiment 1-5 and comparative example 1 and conduction
Additive (Super-P), binding agent (PVDF) carry out 8:1:1 (mass ratio) mixes, and negative plate is obtained by collector of Copper Foil.
With LiPF6It is electrolyte, lithium piece is that positive pole composition half-cell carries out electrochemical property test, tests the matter of the electrode composite material
Amount specific capacity and volume and capacity ratio, acquired results are as shown in table 1.
Table 1：The test result of embodiment 1 to 5 and comparative example 1.
As can be seen from Table 1：With the increase of desulfurization content, material headspace is bigger, while density is smaller.It is accurate to adjust
Control sulfur content, can obtain dense porous three-dimensional graphene framework, meet the cubical expansivity of tin ash 250%, obtain
While obtaining high-quality specific capacity (993mAh/g), volume and capacity ratio (2167mAh/cm high is obtained3)。
Embodiment 6
The specific surface area of three-dimensional porous Graphene-tin ash combination electrode material that the present embodiment is provided is 224m2/ g,
Pore volume is 0.20cm3/ g, block density is 2.34g/cm3, and the volume sum of negative material mesopore is the volume of non-carbon material
2.12 times of sum.
Wherein, non-carbon material is tin ash, and three-dimensional porous Graphene is 1 with the mass ratio of tin ash:2.3.
The preparation method of the negative material is at least comprised the following steps：
The first step, takes 1.5mg/mL modified graphene dispersion liquids 78.5mL and is placed in 100mL beakers, adds 0.76g distillations
Sulphur (is dissolved in 1mL carbon disulfide), and stirring 40min makes it fully react, and is subsequently adding 500mg SnCl4·5H2O, stirring makes
It all dissolves, and obtains mixed dispersion liquid；
Second step, hydro-thermal reaction, water are carried out in the hydrothermal reaction kettle of the mixed dispersion liquid addition 100mL that the first step is obtained
Thermal response temperature is 180 DEG C, and the hydro-thermal duration is 12h, obtains the compound hydrogel of Graphene-tin ash-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, Zhi Hou
Sufficiently drying in 28h hours is carried out at 80 DEG C, by moisture removal, pending product is obtained；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, specifically, under nitrogen protection, with
The heating rate of 15 DEG C/min is warming up to 350 DEG C, then constant temperature 12h, and sulphur is removed, and is cooled to room temperature, obtains three-dimensional porous stone
Black alkene-tin ash combination electrode material.
Embodiment 7
The specific surface area of three-dimensional porous Graphene-tin ash combination electrode material that the present embodiment is provided is 187m2/ g,
Pore volume is 0.17cm3/ g, block density is 2.51g/cm3, and the volume sum of negative material mesopore is the volume of non-carbon material
1.92 times of sum.
Wherein, non-carbon material is tin ash, and three-dimensional porous Graphene is 1 with the mass ratio of tin ash:4.
The preparation method of the negative material is at least comprised the following steps：
The first step, takes 2.5mg/mL porous graphene dispersion liquids 78.5mL and is placed in 100mL beakers, adds 0.75g vulcanizations
Sodium, is subsequently adding 0.5M sulfurous acid 6.5mL, and stirring 50min makes it fully react, is subsequently adding 700mg SnCl4·5H2O, stirs
Mix and uniformly make its all dissolving, obtain mixed dispersion liquid；
Second step, hydro-thermal reaction, water are carried out in the hydrothermal reaction kettle of the mixed dispersion liquid addition 100mL that the first step is obtained
Thermal response temperature is 200 DEG C, and the hydro-thermal duration is 4h, obtains the compound hydrogel of Graphene-tin ash-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, Zhi Hou
12h is carried out at 85 DEG C sufficiently to dry, and by moisture removal, obtains pending product；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, specifically, under nitrogen protection, with
The heating rate of 15 DEG C/min is warming up to 450 DEG C, then constant temperature 20h, and sulphur is removed, and is cooled to room temperature, obtains three-dimensional porous stone
Black alkene-tin ash combination electrode material.
Embodiment 8
The specific surface area of three-dimensional porous Graphene-tin ash combination electrode material that the present embodiment is provided is 257m2/ g,
Pore volume is 0.27cm3/ g, block density is 1.62g/cm3, and the volume sum of negative material mesopore is the volume of non-carbon material
2.82 times of sum.
Wherein, non-carbon material is tin ash, and three-dimensional porous Graphene is 1 with the mass ratio of tin ash:0.6.
The preparation method of the negative material is at least comprised the following steps：
The first step, takes 2.2mg/mL porous graphene dispersion liquids 78.5mL and is placed in 100mL beakers, adds 0.75g vulcanizations
Sodium, is subsequently adding 0.5M sulfurous acid 6.5mL, and stirring 50min makes it fully react, and is subsequently adding 200mg stannous chloride, and stirring is equal
It is even it is all dissolved, obtain mixed dispersion liquid；
Second step, hydro-thermal reaction, water are carried out in the hydrothermal reaction kettle of the mixed dispersion liquid addition 100mL that the first step is obtained
Thermal response temperature is 190 DEG C, and the hydro-thermal duration is 8h, obtains the compound hydrogel of Graphene-tin ash-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, Zhi Hou
Sufficiently drying in 16h hours is carried out at 75 DEG C, by moisture removal, pending product is obtained；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, specifically, by the grinding of pending product
After be placed in carbon disulfide, persistently stir 24h, the sulphur in pending product is completely dissolved in carbon disulfide, obtain three-dimensional
Porous graphene-tin ash combination electrode material.
Comparative example 2
The specific surface area of the three-dimensional porous Graphene that this comparative example is provided is 262m2/ g, pore volume is 0.47cm3/ g, block is close
It is 0.89g/cm to spend3。
In its preparation method, by SnCl in embodiment 64·5H2O consumptions are adjusted to 0mg, and remaining is same as Example 6, this
In repeat no more.
By prepared by embodiment 6-8 and comparative example 2 with three-dimensional porous Graphene-tin ash combination electrode, three-dimensional
Porous graphene carries out 8 with conductive additive (Super-P), binding agent (PVDF):1:1 (mass ratio) mixes, and is with Copper Foil
Collector is obtained negative plate.With LiPF6It is electrolyte, lithium piece is that positive pole composition half-cell carries out electrochemical property test, the electricity
The specific discharge capacity and volume and capacity ratio of pole composite, acquired results are as shown in table 2.
Table 2：The test result of embodiment 6 to 8 and comparative example 2.
As can be seen from Table 2：In the case where the load capacity of sulphur is certain, the content of tin ash active material is higher, close
Degree is higher, but the reserved volume required for it is also higher.Can be with by the size for adjusting tin ash content and reserved volume
Obtain high-volume and capacity ratio.
Embodiment 9
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 342m2/ g, pore volume is 1.03cm3/ g, block density is
0.68g/cm3, and the volume sum of negative material mesopore is 3.56 times of volume sum of non-carbon material.
Wherein, non-carbon material is silicon, and three-dimensional porous Graphene is 1 with the mass ratio of silicon:2.
The preparation method of the negative material is at least comprised the following steps：
The first step, takes 2mg/mL graphene oxide dispersions 78.5mL and is placed in 100mL beakers, adds 0.75g
Na2S2O3·5H2O, is subsequently adding 1M hydrochloric acid 6.5mL, and stirring 30min makes it fully react, is subsequently adding 350mg nano silica fumes,
Stirring makes it all dissolve, and obtains mixed dispersion liquid；
Second step, hydro-thermal reaction, water are carried out in the hydrothermal reaction kettle of the mixed dispersion liquid addition 100mL that the first step is obtained
Thermal response temperature is 150 DEG C, and the hydro-thermal duration is 6h, obtains the compound hydrogel of Graphene-silicon-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, Zhi Hou
Sufficiently drying in 48h hours is carried out at 70 DEG C, by moisture removal, pending product is obtained；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, specifically, under argon gas protection, with
The heating rate of 10 DEG C/min is warming up to 400 DEG C, then constant temperature 6h, and sulphur is removed, and is cooled to room temperature, obtains three-dimensional porous graphite
Alkene-silicon combination electrode material.
Embodiment 10
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 305m2/ g, pore volume is 0.90cm3/ g, block density is
0.75g/cm3, and the volume sum of negative material mesopore is 3.12 times of volume sum of non-carbon material.
Wherein, non-carbon material is silicon, and three-dimensional porous Graphene is 1 with the mass ratio of silicon:2.
In the preparation method of the negative material, as different from Example 9：The consumption of graphene oxide dispersion is adjusted to
83.5mL,Na2S2O3·5H2The consumption of O is adjusted to 0.1g, and hydrochloric acid consumption is adjusted to 1.5mL.Remaining is same as Example 9, this
In repeat no more.
Embodiment 11
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 312m2/ g, pore volume is 0.95cm3/ g, block density is
0.72g/cm3, and the volume sum of negative material mesopore is 3.28 times of volume sum of non-carbon material.
Wherein, non-carbon material is silicon, and three-dimensional porous Graphene is 1 with the mass ratio of silicon:2.
In the preparation method of the negative material, in the preparation method of the negative material, as different from Example 9：Oxidation
Graphene dispersing solution replaces with modified graphene dispersion liquid, and the consumption of modified graphene dispersion liquid is 82.5mL, Na2S2O3·
5H2O replaces with sublimed sulfur (being dissolved in 1mL carbon disulfide), and the consumption of sublimed sulfur is 0.21g, and remaining is same as Example 9, this
In repeat no more.
Embodiment 12
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 355m2/ g, pore volume is 1.06cm3/ g, block density is
0.67g/cm3, and the volume sum of negative material mesopore is 3.65 times of volume sum of non-carbon material.
Wherein, non-carbon material is silicon, and three-dimensional porous Graphene is 1 with the mass ratio of silicon:2.
The preparation method of the negative material is at least comprised the following steps：
The first step, takes 1.5mg/mL porous graphene dispersion liquids 72mL and is placed in 100mL beakers, adds 1.6g vulcanized sodium,
0.5M nitric acid 13mL are subsequently adding, stirring 30min makes it fully react, is subsequently adding 350mg nano silica fumes, and stirring makes it
All dissolving, obtains mixed dispersion liquid；
Second step, hydro-thermal reaction, water are carried out in the hydrothermal reaction kettle of the mixed dispersion liquid addition 100mL that the first step is obtained
Thermal response temperature is 170 DEG C, and the hydro-thermal duration is 15h, obtains the compound hydrogel of Graphene-silicon-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, Zhi Hou
Sufficiently drying in 12h hours is carried out at 85 DEG C, by moisture removal, pending product is obtained；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, specifically, under argon gas protection, with 7
DEG C/heating rate of min is warming up to 420 DEG C, then constant temperature 9h, sulphur is removed, and is cooled to room temperature, obtains three-dimensional porous graphite
Alkene-silicon combination electrode material.
Embodiment 13
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 372m2/ g, pore volume is 0.83cm3/ g, block density is
0.79g/cm3, and the volume sum of negative material mesopore is 2.85 times of volume sum of non-carbon material.
Wherein, non-carbon material is silicon, and three-dimensional porous Graphene is 1 with the mass ratio of silicon:2.
The preparation method of the negative material is at least comprised the following steps：
The first step, takes 2.5mg/mL porous graphene dispersion liquids 55mL and is placed in 100mL beakers, adds 3.4g
Na2S2O3·5H2O, is subsequently adding 1M sulfuric acid 28mL, and stirring 30min makes it fully react, is subsequently adding 350mg nano silica fumes,
Stirring makes it all dissolve, and obtains mixed dispersion liquid；
Second step, hydro-thermal reaction, water are carried out in the hydrothermal reaction kettle of the mixed dispersion liquid addition 100mL that the first step is obtained
Thermal response temperature is 210 DEG C, and the hydro-thermal duration is 5h, obtains the compound hydrogel of Graphene-silicon-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, Zhi Hou
Sufficiently drying in 40h hours is carried out at 65 DEG C, by moisture removal, pending product is obtained；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, specifically, by the grinding of pending product
After be placed in carbon disulfide, persistently stir 36h, the sulphur in pending product is completely dissolved in carbon disulfide, obtain three-dimensional
Porous graphene-tin ash combination electrode material.
Comparative example 3
This comparative example provides a kind of graphene-based lithium ion battery negative material, and negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, its specific surface area is 298m2/ g, pore volume is 0.35cm3/ g, block density is 0.96g/
cm3, and the volume sum of negative material mesopore is 3.56 times of volume sum of non-carbon material.
Wherein, non-carbon material is silicon, and three-dimensional porous Graphene is 1 with the mass ratio of silicon:2.
In its preparation method, and by unlike embodiment 9, Na2S2O3·5H2The consumption of O is adjusted to 0g, hydrochloric acid consumption
It is adjusted to 0mL.Remaining is same as Example 9, repeats no more here.
Three-dimensional porous Graphene-silicon combination electrode material prepared by embodiment 10-13 and comparative example 3 is added with conductive
Agent (Super-P), binding agent (PVDF) carry out 8:1:1 (mass ratio) mixes, and negative plate is obtained by collector of Copper Foil.With
LiPF6It is electrolyte, lithium piece is that positive pole composition half-cell carries out electrochemical property test, the quality specific volume of the electrode composite material
Amount and volume and capacity ratio, as shown in table 3.
Table 3：The test result of embodiment 9 to 13 and comparative example 3.
As can be seen from Table 3：With the increase of desulfurization content, material headspace is bigger, while density is smaller.It is accurate to adjust
Control sulfur content, can obtain dense porous three-dimensional graphene framework, meet the cubical expansivity of silicon 300%, high-quality obtaining
While amount specific capacity (870mAh/g), volume and capacity ratio (618mAh/cm high is obtained3)。
Embodiment 14
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 323m2/ g, pore volume is 0.30cm3/ g, block density is
1.70g/cm3, and the volume sum of negative material mesopore is 2.25 times of volume sum of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and three-dimensional porous Graphene is 1 with the mass ratio of di-iron trioxide:2.
The preparation method of the negative material is at least comprised the following steps：
The first step, takes 2mg/mL graphene oxide dispersions 78.5mL and is placed in 100mL beakers, adds 0.75g
Na2S2O3·5H2O, is subsequently adding 1M hydrochloric acid 6.5mL, and stirring 30min makes it fully react, is subsequently adding 270mg FeCl3·
6H2O, stirring makes it all dissolve, and obtains mixed dispersion liquid；
Second step, hydro-thermal reaction, water are carried out in the hydrothermal reaction kettle of the mixed dispersion liquid addition 100mL that the first step is obtained
Thermal response temperature is 150 DEG C, and the hydro-thermal duration is 6h, obtains the compound hydrogel of Graphene-di-iron trioxide-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, Zhi Hou
Sufficiently drying in 48h hours is carried out at 70 DEG C, by moisture removal, pending product is obtained；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, specifically, under argon gas protection, with
The heating rate of 10 DEG C/min is warming up to 400 DEG C, then constant temperature 6h, and sulphur is removed, and is cooled to room temperature, obtains three-dimensional porous graphite
Alkene-di-iron trioxide combination electrode material.
Embodiment 15
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 292m2/ g, pore volume is 0.27cm3/ g, block density is
1.81g/cm3, and the volume sum of negative material mesopore is 2.02 times of volume sum of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and three-dimensional porous Graphene is 1 with the mass ratio of di-iron trioxide:2.
The preparation method of the negative material is at least comprised the following steps：
The first step, takes 1.5mg/mL porous graphene dispersion liquids 83.5mL and is placed in 100mL beakers, adds 0.1g sublimed sulfurs
(being dissolved in 1mL carbon disulfide), stirring 30min makes it fully react, and is subsequently adding 270mg FeCl3·6H2O, stirring makes it
All dissolving, obtains mixed dispersion liquid；
Second step, hydro-thermal reaction, water are carried out in the hydrothermal reaction kettle of the mixed dispersion liquid addition 100mL that the first step is obtained
Thermal response temperature is 220 DEG C, and the hydro-thermal duration is 8h, obtains the compound hydrogel of Graphene-di-iron trioxide-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, Zhi Hou
Sufficiently drying in 40h hours is carried out at 80 DEG C, by moisture removal, pending product is obtained；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, specifically, under argon gas protection, with 8
DEG C/heating rate of min is warming up to 450 DEG C, then constant temperature 10h, sulphur is removed, and is cooled to room temperature, obtains three-dimensional porous graphite
Alkene-di-iron trioxide combination electrode material.
Embodiment 16
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 305m2/ g, pore volume is 0.29cm3/ g, block density is
1.75g/cm3, and the volume sum of negative material mesopore is 2.15 times of volume sum of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and three-dimensional porous Graphene is 1 with the mass ratio of di-iron trioxide:2.
In the preparation method of the negative material as different from Example 14：By graphene oxide dispersion in embodiment 14
Consumption be adjusted to 82.5mL, Na2S2O3·5H2The consumption of O is adjusted to 0.21g, and hydrochloric acid consumption is adjusted to 2.5mL.Remaining and reality
Apply example 1 identical, repeat no more here.
Embodiment 17
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 328m2/ g, pore volume is 0.31cm3/ g, block density is
1.68g/cm3, and the volume sum of negative material mesopore is 2.36 times of volume sum of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and three-dimensional porous Graphene is 1 with the mass ratio of di-iron trioxide:2.
In the preparation method of the negative material as different from Example 14：By graphene oxide dispersion in embodiment 10
Consumption be adjusted to 72mL, Na2S2O3·5H2The consumption of O is adjusted to 1.6g, and hydrochloric acid consumption is adjusted to 13mL.Remaining and embodiment
1 is identical, repeats no more here.
Embodiment 18
A kind of graphene-based lithium ion battery negative material is present embodiments provided, negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on three-dimensional porous Graphene
Material, negative material has abundant pore structure, and its specific surface area is 345m2/ g, pore volume is 0.33cm3/ g, block density is
1.60g/cm3, and the volume sum of negative material mesopore is 2.51 times of volume sum of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and three-dimensional porous Graphene is 1 with the mass ratio of di-iron trioxide:2.
The preparation method of the negative material is at least comprised the following steps：
The first step, takes 1.5mg/mL modified graphene dispersion liquids 55mL and is placed in 100mL beakers, adds 3.4g vulcanized sodium,
0.5M sulfurous acid 28mL are subsequently adding, stirring 30min makes it fully react, is subsequently adding 270mg FeCl3·6H2O, stirring is equal
It is even it is all dissolved, obtain mixed dispersion liquid；
Second step, hydro-thermal reaction, water are carried out in the hydrothermal reaction kettle of the mixed dispersion liquid addition 100mL that the first step is obtained
Thermal response temperature is 140 DEG C, and the hydro-thermal duration is 15h, obtains the compound hydrogel of Graphene-di-iron trioxide-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, Zhi Hou
Sufficiently drying in 24h hours is carried out at 85 DEG C, by moisture removal, pending product is obtained；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, specifically, by the grinding of pending product
After be placed in carbon disulfide, persistently stir 40h, the sulphur in pending product is completely dissolved in carbon disulfide, obtain three-dimensional
Porous graphene-tin ash combination electrode material.
Comparative example 4
This comparative example provides a kind of graphene-based lithium ion battery negative material, and negative material is three-dimensional porous graphite
Alkene-non-carbon material combination electrode material, its specific surface area is 275m2/ g, pore volume is 0.24cm3/ g, block density is 1.92g/
cm3, and the volume sum of negative material mesopore is 1.85 times of volume sum of non-carbon material.
Wherein, non-carbon material is di-iron trioxide, and three-dimensional porous Graphene is 1 with the mass ratio of di-iron trioxide:2.
Its preparation method is as different from Example 14：By Na in embodiment 142S2O3·5H2The consumption of O is adjusted to 0g,
Hydrochloric acid consumption is adjusted to 0mL.Remaining is identical with embodiment 14, repeats no more here.
By the three-dimensional porous Graphene-tin ash combination electrode material prepared by embodiment 11-18 and comparative example 4 with lead
Electric additive (Super-P), binding agent (PVDF) carry out 8:1:1 (mass ratio) mixes, and negative pole is obtained by collector of Copper Foil
Piece.With LiPF6It is electrolyte, lithium piece is that positive pole composition half-cell carries out electrochemical property test, the matter of the electrode composite material
Amount specific capacity and volume and capacity ratio, acquired results are as shown in table 4.
Table 4：The test result of embodiment 14 to 18 and comparative example 4.
As can be seen from Table 4：With the increase of desulfurization content, material headspace is bigger, while density is smaller.It is accurate to adjust
Control sulfur content, can obtain dense porous three-dimensional graphene framework, meet the cubical expansivity of di-iron trioxide 200%,
While obtaining high-quality specific capacity (589mAh/g), volume and capacity ratio (677mAh/cm high is obtained3)。
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in specific embodiment disclosed and described above, to of the invention
Some modifications and changes should also be as falling into scope of the claims of the invention.Although additionally, being used in this specification
Some specific terms, but these terms are merely for convenience of description, do not constitute any limitation to the present invention.
Claims (10)
1. a kind of graphene-based lithium ion battery negative material, it is characterised in that：The negative material be three-dimensional porous Graphene-
Non-carbon material combination electrode material, it includes three-dimensional porous Graphene and the non-carbon materials being carried on the three-dimensional porous Graphene
Material, the negative material has abundant pore structure, and its specific surface area is 170-400 m2/ g, pore volume is 0.18-1.2 cm3/ g,
Block density is 0.6-3.0 g/cm3, and the negative material mesopore volume sum be the non-carbon material volume it
1.9 times -4 times of sum.
2. graphene-based lithium ion battery negative material according to claim 1, it is characterised in that：The non-carbon material is
At least one in tin ash, silicon and iron oxide.
3. graphene-based lithium ion battery negative material according to claim 1, it is characterised in that：The negative material
In, three-dimensional porous Graphene is 1 with the mass ratio of non-carbon material:(1.6-4).
4. graphene-based lithium ion battery negative material according to claim 1, it is characterised in that the negative material
Preparation method is at least comprised the following steps：
The first step, addition sulphur-containing substance and the acid in graphite alkenes dispersion liquid, and the presoma of non-carbon material is added, fully stir
Mix and obtain mixed dispersion liquid；
Second step, mixed dispersion liquid that the first step is obtained carries out hydro-thermal reaction in adding hydrothermal reaction kettle, obtains Graphene-non-
The compound hydrogel of carbon material-sulphur；
3rd step, the hydrogel that second step is obtained sufficiently is soaked in deionized water, goes the removal of impurity, and water-filling is entered afterwards
Divide removing, obtain pending product；
4th step, desulfurization process are carried out by the pending product that the 3rd step is obtained, and obtain three-dimensional porous Graphene-non-carbon material multiple
Composite electrode material.
5. graphene-based lithium ion battery negative material according to claim 4, it is characterised in that：In the first step, graphite
The mass ratio of the presoma of alkenes dispersion liquid, sulphur-containing substance, acid and non-carbon material is 1:(0.6-18):(0.25-1.5):(1-
4.5), the concentration of the graphite alkenes dispersion liquid is 1-3 mg/mL.
6. graphene-based lithium ion battery negative material according to claim 4, it is characterised in that：It is described in the first step
Graphite alkenes dispersion liquid in graphene oxide dispersion, modified graphene dispersion liquid and porous graphene dispersion liquid at least
It is a kind of；Described sulphur-containing substance is at least one in distillation sulphur simple substance, sodium thiosulfate and vulcanized sodium；It is described acid for hydrochloric acid,
At least one in nitric acid, sulfuric acid, sulfurous acid, carbonic acid and acetic acid；The presoma of described non-carbon material is butter of tin, dichloro
Change at least one in tin, stannic disulfide, silica flour, ferric trichloride.
7. graphene-based lithium ion battery negative material according to claim 4, it is characterised in that：In second step, hydro-thermal
The temperature of reaction is 100oC-250 oC, hydro-thermal reaction duration is 3 h-48 h.
8. graphene-based lithium ion battery negative material according to claim 4, it is characterised in that：In 3rd step, moisture
The method of removing is drying, and drying temperature is 60oC-90 oC, baking duration is 6 h-72 h.
9. graphene-based lithium ion battery negative material according to claim 4, it is characterised in that：In 4th step, desulfurization
It is processed as being heat-treated desulfurization, the method for being heat-treated desulfurization is：Under inert gas shielding atmosphere, with 3-20oThe intensification speed of C/min
Rate is warming up to 300oC-500 oC, then the h-24 h of constant temperature 3, sulphur is removed, and is cooled to room temperature.
10. graphene-based lithium ion battery negative material according to claim 4, it is characterised in that：In 4th step, desulfurization
It is processed as solvent method desulfurization：It is placed in carbon disulfide after pending product is ground, persistently stirs 6 h-48 h, makes pending product
Sulphur in thing is completely dissolved in carbon disulfide.
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| CN108306007A (en) * | 2018-01-31 | 2018-07-20 | 天津大学 | The method that lithium ion cell nano silicium cathode face carrying capacity is improved using sulphur template and Activation of Hydrogen Peroxide Solution |
| CN108364801A (en) * | 2018-01-31 | 2018-08-03 | 天津大学 | A kind of preparation method of graphene-based densified composite |
| CN108365219A (en) * | 2018-01-31 | 2018-08-03 | 天津大学 | A kind of preparation method of graphene-based lithium ion battery negative material |
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