CN109095473A - The low cost preparation method of silica and the low cost preparation method of silicon-carbon cathode material - Google Patents
The low cost preparation method of silica and the low cost preparation method of silicon-carbon cathode material Download PDFInfo
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- CN109095473A CN109095473A CN201810959353.2A CN201810959353A CN109095473A CN 109095473 A CN109095473 A CN 109095473A CN 201810959353 A CN201810959353 A CN 201810959353A CN 109095473 A CN109095473 A CN 109095473A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims description 18
- 239000010406 cathode material Substances 0.000 title claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002893 slag Substances 0.000 claims abstract description 59
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- 239000013049 sediment Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 13
- 239000010959 steel Substances 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 230000001681 protective effect Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 229910001021 Ferroalloy Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052710 silicon Inorganic materials 0.000 abstract description 12
- 239000010703 silicon Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 239000007773 negative electrode material Substances 0.000 abstract description 4
- 230000003628 erosive effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000003513 alkali Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 230000001376 precipitating effect Effects 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 8
- 238000005554 pickling Methods 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
- H01M4/362—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation methods of silica, comprising: S1) slag charge is mixed with hydrochloric acid solution, after filtering, obtain sediment；The slag charge is selected from steel slag and/or clinker；S2 the sediment is mixed with aqueous slkali), is evaporated, obtains filtrate；S3) pH value of the filtrate is adjusted to less than is equal to 7, filtering after calcining, obtains silica.Compared with prior art, the present invention is using steel slag as raw material, first with the erosion of acid, impurity metal oxide is removed, the higher silica of purity can be obtained by reconciling the pH value of solution in remaining precipitation of silica object, and preparation method is simple, it is environmental-friendly, and extraction content is higher, and the novel silicon base negative electrode material of lithium ion battery is used to prepare using the silica extracted, reduces production cost.
Description
Technical field
The invention belongs to the low cost preparation methods and silicon-carbon cathode of battery technology field more particularly to a kind of silica
The low cost preparation method of material.
Background technique
Lithium ion battery has high energy density, longer service life cycle and low self-discharge rate, is widely applied
In smart phone, portable computer, electric car etc., have become the hot spot of scientific research.With the development of human society,
People have higher requirement for the lithium ion battery of commercialization, need higher energy density, specific capacity and service life,
Need material source extensive simultaneously, it is cheap and safe and reliable.Currently, used in the lithium ion secondary battery of commercialization
Negative electrode material is mainly graphite carbon material.However, graphite theoretical capacity is low (372mAh/g), and holds in quick process of intercalation
Analysis lithium phenomenon easily occurs, safety is poor, is difficult meet the needs of people are to high capacity power source.
Silica-base material is the hot spot studied at present, it is considered to be a kind of very promising carbons negative electrode material substitute.
The theoretical capacity of pure silicon is a kind of ideal negative electrode material up to 4200mAh/g, the significantly larger than theoretical capacity of graphite.
But elemental silicon volume expansion in charge and discharge process is serious (> 300%), causes electrode material breaking and Dusting, cycle performance drop
It is low.Also, elemental silicon is expensive, and preparation cost is higher, is difficult meet the needs of commercial applications.Therefore, it finds cheap
Silicon source, and solve the problems, such as that the cyclical stability of silicon is the huge challenge that current silicon based cells commercialization process faces.
In general, the expansion issues of silicon-based anode can be by preparing porous structure material, cladding carbon material, doping etc.
Method solves.Studies have shown that by elemental silicon and carbon material carry out it is compound can not only obtain higher capacity, while can also delay
The volume expansion for solving silicon, improves the cycle life of battery.But it is but more difficult to find suitable silicon source.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of silica preparation method and silicon-carbon it is negative
The preparation method of pole material, the preparation method is simple and cost is relatively low.
The present invention provides a kind of preparation methods of silica, comprising:
S1 slag charge is mixed with hydrochloric acid solution), after filtering, obtains sediment；The slag charge is selected from steel slag and/or clinker；
S2 the sediment is mixed with aqueous slkali), filters, obtains filtrate；
S3) pH value of the filtrate is adjusted to less than or equal to 7, is evaporated, after calcining, obtains silica.
Preferably, the content of aluminum oxide is less than or equal to 20wt% in the slag charge；The content of ferroalloy is less than or equal to
25wt%；The content of silica is more than or equal to 10wt%.
Preferably, the step S1) in mixed again with hydrochloric acid solution after slag charge ball milling.
Preferably, the ratio of grinding media to material when ball milling is (5~30): 1；The revolving speed of the ball milling is 100~1000rpm.
Preferably, the concentration of the hydrochloric acid solution is 0.1~5mol/L；The mass volume ratio of the slag charge and hydrochloric acid solution
Less than or equal to 1g:2.5ml.
Preferably, the step S1) in mix time be 0.5~10h.
Preferably, the step S2) in alkaline concentration be 0.1~1mol/L；The mass body of the slag charge and aqueous slkali
Product is than being 1g:(100~500) ml.
Preferably, the step S2) in mix temperature be 40 DEG C~80 DEG C；The mixed time is 1~12h.
Preferably, the step S3) in calcine temperature be 150 DEG C~600 DEG C；The time of calcining is 1~6h.
The present invention also provides a kind of preparation methods of silicon-carbon cathode material, comprising:
S1 slag charge is mixed with hydrochloric acid solution), after filtering, obtains sediment；The slag charge is selected from steel slag and/or clinker；
S2 the sediment is mixed with aqueous slkali), filters, obtains filtrate；
S3) pH value of the filtrate is adjusted to less than is equal to 7, filtering after calcining, obtains silica；
S4 magnesiothermic reduction, the product after being restored are carried out after) mixing the silica with magnesium metal；
S5 it after) mixing the product after the reduction with graphite, is impregnated in acid solution, obtains mixture；
S6 it after) mixing the mixture with organic carbon source, is calcined in protective atmosphere, obtains silicon-carbon cathode material.
The present invention provides a kind of preparation methods of silica, comprising: S1) slag charge is mixed with hydrochloric acid solution, it filters
Afterwards, sediment is obtained；The slag charge is selected from steel slag and/or clinker；S2 the sediment is mixed with aqueous slkali), is evaporated, obtains
Filtrate；S3) pH value of the filtrate is adjusted to less than is equal to 7, filtering after calcining, obtains silica.With the prior art
It compares, the present invention first with the erosion of acid, removes impurity metal oxide, remaining silica is heavy using steel slag as raw material
The higher silica of purity can be obtained by reconciling the pH value of solution in starch, and preparation method is simple, environmental-friendly, and mentions
It takes content higher, the novel silicon-carbon cathode material of lithium ion battery is used to prepare using the silica extracted, reduces life
Produce cost.
Detailed description of the invention
Fig. 1 is the XRD spectra of precipitating obtained in the embodiment of the present invention 1；
Fig. 2 is the XRD spectra of filter residue obtained in the embodiment of the present invention 1；
Fig. 3 is the XRD spectra of silica obtained in the embodiment of the present invention 1；
Fig. 4 is the XRD spectra of filter residue obtained in the embodiment of the present invention 2；
Fig. 5 is the XRD spectra of precipitating obtained in the embodiment of the present invention 5；
Fig. 6 is the XRD spectra of precipitating obtained in the embodiment of the present invention 6；
Fig. 7 is the charge and discharge cycles curve graph of silicon-carbon cathode material obtained in the embodiment of the present invention 8.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of preparation methods of silica, comprising:
S1 slag charge is mixed with hydrochloric acid solution), after filtering, obtains sediment；The slag charge is selected from steel slag and/or clinker；
S2 the sediment is mixed with aqueous slkali), filters, obtains filtrate；
S3) pH value of the filtrate is adjusted to less than equal to 7, is evaporated, after calcining, obtains silica.
The present invention is not particularly limited the source of all raw materials, for commercially available or self-control.
Wherein, the slag charge is steel slag well known to those skilled in the art and/or clinker, has no special limitation,
Discarded blast furnace slag, vessel slag and one of the slag or a variety of of boiling preferably are made steel in the present invention；Three oxidation in the slag charge
The content of two aluminium is preferably smaller than equal to 20wt%, more preferably less than or equal to 15wt%, more preferably less than equal to 12wt%；Ferroalloy
Content preferably smaller than be equal to 25wt%, more preferably less than or equal to 20wt%；The content of silica is preferably greater than or equal to
10wt%, more preferably 10wt%~30wt% are further preferably 10wt%~20wt%；The content of calcium oxide is excellent in the slag charge
It is further preferably 30~52wt% that choosing, which is less than or equal to 60wt% more preferably less than or equal to 55wt%,；Magnesia contains in the slag charge
Amount is preferably smaller than equal to 20wt%, more preferably less than or equal to 18wt%；The content of manganese oxide is preferably smaller than equal in the slag charge
10wt%, more preferably less than or equal to 8wt%；The content of phosphorus pentoxide is preferably smaller than equal to 5wt% in the slag charge；The slag
The content of sulphur is preferably smaller than equal to 1wt% in material, more preferably less than or equal to 0.5wt%, more preferably less than equal to 0.2wt%.
According to the present invention, the slag charge preferably first carries out ball milling；The ratio of grinding media to material when ball milling is preferably (5~30): 1,
More preferably (5~25): 1, it is further preferably (5~20): 1, most preferably (10~15): 1；The revolving speed of the ball milling is preferably
100~1000rpm, more preferably 200~800rpm are further preferably 300~600rpm, most preferably 400~500rpm；It is described
The time of ball milling is preferably 3~10h, more preferably 4~8h, is further preferably 5~7h, most preferably 6h；The ball milling preferably makes
The partial size of slag charge is less than or equal to 100 mesh, is more preferably less than equal to 80 mesh, most preferably small further preferably for less than or equal to 60 mesh
In equal to 40 mesh.
Slag charge after ball milling is mixed with hydrochloric acid solution；The hydrochloric acid solution is that hydrochloric acid well known to those skilled in the art is molten
Liquid has no special limitation, and the concentration of heretofore described hydrochloric acid solution is preferably 0.1~5mol/L, and more preferably 0.1
~3mol/L is further preferably 0.1~1mol/L, most preferably 0.5~1mol/L；The quality of slag charge and hydrochloric acid after the ball milling
Volume ratio is preferably smaller than equal to 1g:2.5ml, more preferably 1g:(2.5~50) ml, be further preferably 1g:(5~50) ml；It is described mixed
Conjunction preferably carries out at room temperature；The mixing, which preferably uses, to be stirred；The mixed time is preferably 0.5~10h,
More preferably 0.5~6h is further preferably 0.5~4h, is further preferably 0.5~2h, most preferably 0.5~1h.
After mixing, filtering obtains sediment.
The sediment is mixed with aqueous slkali；The aqueous slkali is aqueous slkali well known to those skilled in the art,
Have no special property, the preferably aqueous solution of alkali metal hydroxide in the present invention, more preferably sodium hydrate aqueous solution and/
Or potassium hydroxide aqueous solution；The concentration of the aqueous slkali is preferably 0.1~1mol/L, more preferably 0.3~0.8mol/L, then excellent
It is selected as 0.5~0.6mol/L；The mass volume ratio of the slag charge and aqueous slkali is preferably 1g:(100~500) ml, more preferably
1g:(100~400) ml, be further preferably 1g:(150~300) ml, most preferably 1g:(150~200) ml；The mixing is preferred
It carries out under heating conditions；The mixed temperature is preferably 40 DEG C~80 DEG C, more preferably 60 DEG C~80 DEG C；The mixing
Time be preferably 1~12h, more preferably 2~10h is further preferably 3~8h, most preferably 3~5h.
After mixing, filtering obtains filtrate and filter residue；The filtrate is silicate solutions, therefore by the pH value of the filtrate
It is adjusted to less than equal to 7, it is preferred to use its pH value is adjusted to less than is equal to 7 by hydrochloric acid solution, and it is molten to be converted into silicic acid
Liquid or silica sol；The concentration of the hydrochloric acid solution is preferably 5~20mol/L, more preferably 5~15mol/L, is further preferably 10
~12mol/L；The preferred pH value for adjusting filtrate is 2~7, more preferably 5~7 in the present invention；Due in obtained filter residue also
Containing silica, therefore preferably continued to mix with aqueous slkali, repeat step S2)；The duplicate number is preferably 1~
5 times, more preferably 1~3 time.
After filtrate is adjusted to less than is equal to 7, it is evaporated, preferably washes, to remove foreign ion, then calcine, obtain two
Silica；The temperature of the calcining is preferably 150 DEG C~600 DEG C, more preferably 150 DEG C~400 DEG C, further preferably for 200 DEG C~
300℃；The time of calcining is preferably 1~6h, more preferably 2~4h.
The present invention, first with the erosion of acid, removes impurity metal oxide, remaining silica using steel slag as raw material
The higher silica of purity can be obtained by reconciling the pH value of solution in sediment, and preparation method is simple, environmental-friendly, and
It is higher to extract content, the novel silicon-carbon cathode material of lithium ion battery is used to prepare using the silica extracted, is reduced
Production cost.
The present invention also provides a kind of preparation methods of silicon-carbon cathode material, comprising: S1) slag charge and hydrochloric acid solution are mixed
It closes, after filtering, obtains sediment；The slag charge is selected from steel slag and/or clinker；S2) sediment is mixed with aqueous slkali, mistake
Filter, obtains filtrate；S3) pH value of the filtrate is adjusted to less than is equal to 7, filtering after calcining, obtains silica；S4)
Magnesiothermic reduction, the product after being restored are carried out after the silica is mixed with magnesium metal；S5) by the production after the reduction
It after object is mixed with graphite, is impregnated in acid solution, obtains mixture；S6 it after) mixing the mixture with organic carbon source, is protecting
It is calcined in shield atmosphere, obtains silicon-carbon cathode material.
Wherein, the step S1)~step S3) it is same as above, details are not described herein.
Magnesiothermic reduction, the product after being restored are carried out after the silica is mixed with magnesium metal；The magnesium metal
Preferably magnesium powder；The mass ratio of the silica and magnesium metal is preferably 10:(5~15), more preferably 10:(5~12), then
Preferably 10:(7~10), most preferably 10:8；The mixed method is method well known to those skilled in the art, and
It is preferably ball milling in the present invention without special limitation；The ratio of grinding media to material of the ball milling is preferably (5~20): 1, more preferably (8~
15): 1, it is further preferably (10~12): 1, most preferably 10:1；The revolving speed of the ball milling is preferably 100~500rpm, more preferably
For 300~500rpm；The time of the ball milling is preferably 3~for 24 hours；The ball milling carries out preferably in protective atmosphere；The guarantor
Shield atmosphere is protective atmosphere well known to those skilled in the art, has no special limitation, is preferably argon gas in the present invention；Institute
The temperature for stating magnesiothermic reduction is preferably 500 DEG C~1000 DEG C, more preferably 600 DEG C~800 DEG C, most preferably 700 DEG C；The magnesium
The time of thermal reduction is preferably 1~10h, more preferably 2~8h, is further preferably 4~6h；The heating rate of the magnesiothermic reduction is excellent
It is selected as 5~15 DEG C/min；The magnesiothermic reduction carries out preferably in protective atmosphere；The protective atmosphere is those skilled in the art
Well known protective atmosphere has no special limitation, is preferably argon gas in the present invention.
Product after the reduction is mixed with graphite；The mass ratio of product and graphite after the reduction is preferably 20:
(5~20), more preferably 20:(8~15), be further preferably 20:(10~13), most preferably 20:11；The mixed method is
Method well known to those skilled in the art has no special limitation, is preferably ball milling in the present invention；The ball material of the ball milling
Than preferably (5~20): 1, more preferably (8~15): 1, it is further preferably (10~12): 1, most preferably 10:1；The ball milling
Revolving speed be preferably 100~500rpm, more preferably 300~500rpm；The time of the ball milling is preferably 3~for 24 hours；The ball
Mill carries out preferably in protective atmosphere；The protective atmosphere is protective atmosphere well known to those skilled in the art, has no spy
Different limitation, the present invention in preferably argon gas.
It after mixing, is impregnated in acid solution, obtains mixture；The acid solution is that acid well known to those skilled in the art is molten
Liquid has no special limitation, is preferably one of hydrochloric acid, phosphoric acid and sulfuric acid or a variety of in the present invention；The acid solution
Concentration be preferably 1~6mol/L, more preferably 1~4mol/L is further preferably 1~3mol/L；Product after the reduction with
The gross mass of graphite and the volume ratio of acid solution are preferably 1g:(80~120) ml；The temperature of the immersion is preferably 20 DEG C~
100 DEG C, more preferably 20 DEG C~80 DEG C, be further preferably 30 DEG C~60 DEG C；The time of the immersion is preferably 1~12h, more preferably
It is further preferably 5~8h for 3~10h；After preferably washing drying after immersion, mixture is obtained.
The mixture is mixed with organic carbon source；The organic carbon source is organic carbon source well known to those skilled in the art
, have no special limitation, in the present invention preferably pitch, polyacrylonitrile, polyvinyl chloride, maltose, sucrose, dopamine,
One of cellulose and covalent organic framework polymer material are a variety of；The mass ratio of the mixture and organic carbon source is preferred
For 6:(1~20), more preferably 6:(3~15), it is further preferably 6:(3~10) and, most preferably 6:(5~7)；The mixed side
Method is method well known to those skilled in the art, has no special limitation, is preferably ball milling in the present invention；The ball milling
Ratio of grinding media to material is preferably (5~20): 1, more preferably (8~15): 1, it is further preferably (10~12): 1, most preferably 10:1；It is described
The revolving speed of ball milling is preferably 100~500rpm, more preferably 300~500rpm；The time of the ball milling is preferably 3~for 24 hours；Institute
Ball milling is stated to carry out preferably in protective atmosphere；The protective atmosphere is protective atmosphere well known to those skilled in the art, and
It is preferably argon gas in the present invention without special limitation.
It after mixing, is calcined in protective atmosphere, obtains silicon-carbon cathode material；The protective atmosphere is those skilled in the art
Well known protective atmosphere has no special limitation, is preferably argon gas in the present invention；The temperature of the calcining is preferably 500
DEG C~1000 DEG C, more preferably 600 DEG C~900 DEG C, be further preferably 700 DEG C~900 DEG C, most preferably 800 DEG C；The calcining
Heating rate is preferably 5~15 DEG C/min；The time of the calcining is preferably 1~12h, more preferably 1~10h, is further preferably 2
~8h is further preferably 4~6h, most preferably 4h.
In order to further illustrate the present invention, with reference to embodiments to a kind of low cost of silica provided by the invention
Preparation method and the low cost preparation method of silicon-carbon cathode material are described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
Using boiling furnace slag as raw material, the ingredient of the boiling furnace slag is shown in Table 1.
The component of 1 boiling furnace slag of table
1.1, by 4g boiling furnace slag ball milling 6h, ratio of grinding media to material 10:1, revolving speed 400rpm, obtain raw material of the granularity less than 40 mesh.
The hydrochloric acid mixed at room temperature of raw material obtained in 2g 1.1 and 100ml0.1mol/L are stirred 0.5~1h by 1.2, are filtered,
It gets a yellowish precipitate.
Precipitating obtained in 2g 1.2 and the sodium hydroxide solution of 300ml0.5mol/L are mixed and heated to 60 DEG C by 1.3,3h
After filter, obtain filter residue and filtrate.
Hydrochloric acid to the pH value that 10mol/L is added dropwise in 1.4 filtrates obtained in 1.3 is 7, is evaporated water for 130 DEG C in an oven
Point, it is dried again after washing, is placed in 200 DEG C of calcining 2h in Muffle furnace, obtains 0.4450g silica, purity 90%.
Filter residue obtained in 1.3 is repeated step 1.3 and 1.4 by 1.5, obtains 0.1350g silica, purity 91%.
It is analyzed using X-ray diffraction to precipitating obtained in 1.2, obtains its XRD spectra, as shown in Figure 1.By Fig. 1
As it can be seen that several apparent diffraction maximums are SiO2Diffraction maximum, wherein mark black dot label diffraction maximum be insoluble impurity
Peak.
Filter residue obtained in 1.4 is analyzed using X-ray diffraction, obtains its XRD spectra, as shown in Figure 2.By Fig. 2
With Ca (Al2Si2O8) standard card compare, find position that unknown impurity peaks occur and its coincide substantially, it may be determined that
There are also the presence of Si in insoluble impurity.
Silica obtained in 1.4 is analyzed using X-ray diffraction, obtains its XRD spectra, as shown in figure 3, by
For Fig. 3 it is found that it is essentially unbodied silica, other impurities content is lower than detection limit.
Embodiment 2
2.1, by 4g boiling furnace slag ball milling 6h, ratio of grinding media to material 10:1, revolving speed 400rpm, obtain raw material of the granularity less than 40 mesh.
The hydrochloric acid mixed at room temperature of raw material obtained in 2g 2.1 and 100ml 0.1mol/L are stirred 0.5~1h by 2.2, are taken out
Filter, gets a yellowish precipitate.
Precipitating obtained in 2g 2.2 and the sodium hydroxide solution of 300ml 0.1mol/L are mixed and heated to 80 DEG C by 2.3,
It is filtered after 5h, obtains filter residue and filtrate.
Hydrochloric acid to the pH value that 10mol/L is added dropwise in 2.4 filtrates obtained in 2.3 is 7, is evaporated water for 130 DEG C in an oven
Point, it is dried again after washing, is placed in 200 DEG C of calcining 2h in Muffle furnace, obtains 0.3639g silica, purity 86%.
Filter residue obtained in 2.3 is repeated step 2.3 and 2.4 by 2.5, obtains 0.2005g silica, purity 89%.
Filter residue obtained in step 2.3 is analyzed using X-ray diffraction, obtains its XRD spectra, as shown in Figure 4.By
Fig. 4 is it is found that still include the SiO of major part in filter residue2, illustrate that sodium hydroxide solution can not be by silica at normal temperature
It is completely dissolved, and can be seen that unknown impurity peaks still have after through overpickling and alkali soluble, illustrate that impurity did not both dissolve in
Acid is also insoluble in alkali.
Embodiment 3
Precipitating obtained in 2g step 1.2 is mixed with 300ml 0.1mol/L sodium hydroxide solution, carries out first time alkali
It is molten, filter residue is subjected to second of alkali soluble, the filter residue that second of alkali soluble is obtained carries out third time alkali soluble, three times the condition of alkali soluble,
Environment is all the same, is 80 DEG C, and the quality of 5h, obtained silica are shown in Table 2, with step with embodiment 1.
The quality for the silica that 2 alkali soluble of table obtains
| Precipitate quality | 2g |
| The silica quality that first time alkali soluble obtains | 0.3390g |
| The silica quality that second of alkali soluble obtains | 0.2048g |
| The silica quality that third time alkali soluble obtains | 0.1648g |
| The quality for the silica being always obtained | 0.7086g |
The calcined product of alkali soluble three times is analyzed using X-ray diffraction, what is found is amorphous dioxy
The mass content (accounting for deposit sample gross mass) of SiClx, the silica extracted by alkali soluble three times alreadys exceed 30%, reaches
35.43%.
In order to determine the repeatability of experiment, alkali soluble three times is carried out to precipitating obtained in step 1.2 again, condition is constant,
It obtains the results are shown in Table 3.
The quality for the silica that 3 alkali soluble of table obtains
| Precipitate quality | 2g |
| The silica quality that first time alkali soluble obtains | 0.3639g |
| The silica quality that second of alkali soluble obtains | 0.2005g |
| The silica quality that third time alkali soluble obtains | 0.1380g |
| The quality for the silica being always obtained | 0.7024g |
| Mass content (percentage composition for accounting for precipitating quality) | 35.12% |
Prove that SiO2 content is even higher really 35% or so in boiling slag.
Embodiment 4
Precipitating obtained in 2g step 1.2 is mixed with 300ml 1mol/L sodium hydroxide solution, carries out first time alkali soluble,
Filter residue is subjected to second of alkali soluble, the temperature of alkali soluble is 80 DEG C, 5h, remaining step with embodiment 1, obtained silica it is total
Quality is 0.8437g, accounts for the 42% of precipitating quality.
SiO under heating condition in purification boiling slag2Yield it is still more optimistic, and the solution heated is taken out
Filter, due to precipitating coagulation, suction filtration speed is also very fast, filters 300ml at normal temperature and needs 40 minutes or so, but adds
It carries out filtering again after heat and only needs ten minutes, can also be improved efficiency for this angle.
Embodiment 5
By the stirring progress pickling of the hydrochloric acid mixed at room temperature of raw material obtained in 2g 1.1 and 1mol/L, the time of pickling is
6h, 3h, 1h and 0.5h, pickling the results are shown in Table 4.
4 pickling result of table
| 70ml | 50ml | 20ml | 10ml | 5ml | |
| 6h | √ | √ | √ | √ | √ |
| 3h | - | - | - | √ | × |
| 1h | - | - | - | √ | × |
| 0.5h | - | - | - | √ | - |
In table, what √ was represented is precipitating satisfactory quality, and × representative is that precipitating quality is overweight, i.e., soluble impurity does not have
It completely removes, is the side that pickling is ideal and saves wherein the removal of soluble impurity can be completed in 10ml, 0.5h
Case.
Obtained precipitating is analyzed using XRD x ray diffraction, it is as shown in Figure 5 to obtain map.As seen from Figure 5,
The hydrochloric acid that 5ml or more is added in 2g slag specimen can remove wherein soluble impurity, above be 5ml acid in Fig. 5
The precipitating washed, the precipitating obtained below for 70ml pickling.
Embodiment 6
Comparative test is carried out to the chlorohydric acid pickling of various concentration, as a result as shown in fig. 6, precipitating quality is on the left side 1.6g
The right side accounts between the 76%~81% of initial sample gross mass, belongs to normal level, and three done group comparative experiments is added
The amount (molal quantity) of the substance of hydrochloric acid be it is identical, soluble impurity can be removed as seen from the figure, therefore conclusion can be obtained,
In acid cleaning process, relationship is not too big to the concentration of the degree of impurity removal and hydrochloric acid in a certain range, but from technology
Angle considers, since the filtrate after pickling is discharged as waste liquid, then the lesser hydrochloric acid 0.1mol/L of concentration should be selected
As etchant solution, this has certain meaning to subsequent processing and reduction pollution.
Embodiment 7
Alkali soluble step is explored, first alkali soluble when the quality of NaOH that is added, due to SiO2Solution rate and alkali
Concentration and the temperature and time of reaction have relationship, therefore have chosen NaOH concentration as 0.1mol/L, 0.5mol/L, 1mol/L work
For level amount, temperature chooses 80 DEG C, 60 DEG C, 40 DEG C and is used as horizontal amount, and the time chooses 5h, 3h, 1h as level amount, orthogonal test
As shown in table 5.
5 alkali soluble orthogonal experiment of table
When due to alkali soluble, SiO2Meltage size it is related with the concentration of time-temperature and alkali, although the concentration of alkali is got over
Height, temperature is higher, the alkali soluble time is longer, SiO2The affirmative of dissolution is more, but square from the safety of experiment and cost etc.
Face comprehensively considers, and according to the Comparative result of many experiments, it was demonstrated that, it is 60 DEG C in temperature, the concentration of alkali is 0.5mol/L, alkali soluble
When time is 3h, obtained SiO2Amount it is ideal, since work before can obtain SiO after multiple alkali soluble2Quality
About in 0.8g or so, and 0.5780g SiO can be obtained according to above-mentioned 2 alkali solubles of experimental program progress2。
Embodiment 8
By SiO obtained in embodiment 12With magnesium powder with the quality of 10:8 than ball milling mixing, then in argon atmosphere, 700
4h is roasted under the conditions of DEG C；It is down to magnesiothermic reduction product and graphite after room temperature with the quality of 20:11 than ball milling mixing, it is then used
Measure the hcl corrosion (sour dosage is excessive, corresponding 80~120 milliliters of the hydrochloric acid of every gram of material substantially) of 1M, filtering and washing after 5h
After be dried in vacuo；By obtained desciccate and carbon source (sucrose) with the quality of 6:5 than ball milling mixing, in inert atmosphere, 800
High-temperature roasting is carbonized 4 hours under the conditions of DEG C, and silicon-carbon cathode material is obtained after being down to room temperature.All of above mechanical milling process is in argon
In gas atmosphere, and ratio of grinding media to material is 10:1, rotational speed of ball-mill 400rpm, the 4 hours time of ball milling.
Assembly battery: silicon-carbon cathode material obtained in embodiment 8, conductive agent SP and binder PVdF (mass ratio are weighed
8:1:1), it is added appropriate solvent NMP, magnetic agitation is for 24 hours under confined conditions for room temperature.Then it will be stirred with scraper (or automatic film applicator)
It mixes rear slurry to be evenly coated on copper foil, temperature is down to room temperature and takes out pole piece after dry 15h under 120 DEG C of vacuum condition, with punching
Piece machine-cut then stands 30s under the pressure of 20MPa, finally obtains sample electrode at round pole piece (diameter is about 13mm).
It is the sample electrode to electrode, after proportion for Electrode with metal Li piece, diaphragm Celgard2400,
Electrolyte is the 1mol/L LiPF comprising EC/DMC (volume ratio 1:1)6Solution is finally assembling to the button cell of 2032 types.
The battery installed is stood for 24 hours under normal temperature conditions.The current density of charge and discharge is set as 100-170mA/g (root
According to the quality of active material), charging/discharging voltage range is 0.01~3V, and test temperature is 25 DEG C, and the charge and discharge of battery can be obtained
Electric cyclic curve, as shown in Figure 7.
As seen from Figure 7, the discharge capacity for the first time for the silicon-carbon cathode material that embodiment 8 is prepared is 1038.1mAh/
G, charging capacity 751mAh/g, coulombic efficiency is 72.3% for the first time.After recycling 50 weeks, battery reversible capacity is 709mAh/g.
It can be seen that passing through the addition of amorphous carbon and graphite, realizes porous silicon/graphite/carbon clad structure, alleviate elemental silicon and follow
The expansion issues of ring process.
Claims (10)
1. a kind of preparation method of silica characterized by comprising
S1 slag charge is mixed with hydrochloric acid solution), after filtering, obtains sediment；The slag charge is selected from steel slag and/or clinker；
S2 the sediment is mixed with aqueous slkali), filters, obtains filtrate；
S3) pH value of the filtrate is adjusted to less than or equal to 7, is evaporated, after calcining, obtains silica.
2. preparation method according to claim 1, which is characterized in that in the slag charge content of aluminum oxide be less than etc.
In 20wt%；The content of ferroalloy is less than or equal to 25wt%；The content of silica is more than or equal to 10wt%.
3. preparation method according to claim 1, which is characterized in that the step S1) in after slag charge ball milling again with hydrochloric acid
Solution mixing.
4. preparation method according to claim 3, which is characterized in that the ratio of grinding media to material when ball milling is (5~30): 1；Institute
The revolving speed for stating ball milling is 100~1000rpm.
5. preparation method according to claim 1, which is characterized in that the concentration of the hydrochloric acid solution is 0.1~5mol/L；
The mass volume ratio of the slag charge and hydrochloric acid solution is less than or equal to 1g:2.5ml.
6. preparation method according to claim 1, which is characterized in that the step S1) in mix time be 0.5~
10h。
7. preparation method according to claim 1, which is characterized in that the step S2) in alkaline concentration be 0.1~
1mol/L；The mass volume ratio of the slag charge and aqueous slkali is 1g:(100~500) ml.
8. preparation method according to claim 1, which is characterized in that the step S2) in mix temperature be 40 DEG C~
80℃；The mixed time is 1~12h.
9. preparation method according to claim 1, which is characterized in that the step S3) in calcine temperature be 150 DEG C~
600℃；The time of calcining is 1~6h.
10. a kind of preparation method of silicon-carbon cathode material characterized by comprising
S1 slag charge is mixed with hydrochloric acid solution), after filtering, obtains sediment；The slag charge is selected from steel slag and/or clinker；
S2 the sediment is mixed with aqueous slkali), filters, obtains filtrate；
S3) pH value of the filtrate is adjusted to less than is equal to 7, filtering after calcining, obtains silica；
S4 magnesiothermic reduction, the product after being restored are carried out after) mixing the silica with magnesium metal；
S5 it after) mixing the product after the reduction with graphite, is impregnated in acid solution, obtains mixture；
S6 it after) mixing the mixture with organic carbon source, is calcined in protective atmosphere, obtains silicon-carbon cathode material.
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| CN109954494A (en) * | 2017-12-14 | 2019-07-02 | 财团法人工业技术研究院 | Porous material and preparation method and the carbon monoxide-olefin polymeric comprising it |
| CN109954494B (en) * | 2017-12-14 | 2022-05-13 | 财团法人工业技术研究院 | Porous material, preparation method thereof and catalyst composition containing same |
| CN112299423A (en) * | 2019-08-01 | 2021-02-02 | 新特能源股份有限公司 | Silicon dioxide preparation method and prepared silicon dioxide |
| CN112299423B (en) * | 2019-08-01 | 2022-06-28 | 新特能源股份有限公司 | Silicon dioxide preparation method and prepared silicon dioxide |
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Application publication date: 20181228 |