CN111354925B - 具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的合成 - Google Patents
具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的合成 Download PDFInfo
- Publication number
- CN111354925B CN111354925B CN201811575295.XA CN201811575295A CN111354925B CN 111354925 B CN111354925 B CN 111354925B CN 201811575295 A CN201811575295 A CN 201811575295A CN 111354925 B CN111354925 B CN 111354925B
- Authority
- CN
- China
- Prior art keywords
- carbon
- lithium ion
- ion conductor
- fiber structure
- carbon fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 67
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000010416 ion conductor Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000002861 polymer material Substances 0.000 claims abstract description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 14
- 239000004917 carbon fiber Substances 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000005011 phenolic resin Substances 0.000 claims description 27
- 239000010405 anode material Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000011268 mixed slurry Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 16
- 229920001568 phenolic resin Polymers 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229920000620 organic polymer Polymers 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical group [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims description 2
- 229910007822 Li2ZrO3 Inorganic materials 0.000 claims description 2
- 229910012725 Li3N-LiCl Inorganic materials 0.000 claims description 2
- 229910012599 Li3NbO4 Inorganic materials 0.000 claims description 2
- 229910012718 Li3N—LiCl Inorganic materials 0.000 claims description 2
- 229910011312 Li3VO4 Inorganic materials 0.000 claims description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims description 2
- 229910001305 LiMPO4 Inorganic materials 0.000 claims description 2
- 229910003327 LiNbO3 Inorganic materials 0.000 claims description 2
- 229910012985 LiVO3 Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical group [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 150000003346 selenoethers Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- -1 ion compound Chemical class 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 13
- 238000007599 discharging Methods 0.000 abstract description 11
- 230000008859 change Effects 0.000 abstract description 5
- 238000007600 charging Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000000872 buffer Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 15
- 238000000498 ball milling Methods 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002931 mesocarbon microbead Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011363 dried mixture Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910006877 Li1+xMxTi2-x(PO4)3 Inorganic materials 0.000 description 1
- 229910006882 Li1+xMxTi2−x(PO4)3 Inorganic materials 0.000 description 1
- 229910011122 LiM2(PO4)3 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
- D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2101/00—Inorganic fibres
- D10B2101/10—Inorganic fibres based on non-oxides other than metals
- D10B2101/12—Carbon; Pitch
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/0071—Oxides
-
- 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
本发明涉及一种具有碳纤维结构的碳绑定的锂离子导体‑碳复合负极材料及其制备方法,本方法制备的材料颗粒内部是由锂离子导体小晶体和碳负极活性材料小微粒经过碳纤维绑定形成,提高了材料的充放电电流密度。碳纤维有很高的抗拉强度和纤维柔软性,在一定程度上缓冲了材料在充放电过程中发生的体积变化、粉化和团聚,还有效防止被绑定的碳小微粒在长期循环充放电条件下剥离成多层石墨,从而提高了电极的循环稳定性,提高材料的倍率性能,并具有较大的容量。本材料的生产工艺流程短,成本低,对制成的混合颗粒进行高温处理时,高分子材料被碳化成具有碳纤维结构的三维碳纤维网,把锂离子导体和碳小微粒捆绑在同一颗粒中,实现材料生产的一步完成。
Description
技术领域
本发明涉及一种具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,并把该材料用作锂离子电池的负极材料。
背景技术
随着锂离子电池技术在电动车行业、航空产业、电子设备等方面的运用日益增多,人们对锂离子电池的性能提出了更高的要求,而电极材料是提高锂离子电池性能的关键性因素。在负极材料方面,目前商业化的锂离子电池负极材料大多都是石墨,石墨的理论嵌锂容量为372mAh/g,其结晶完整并具有高取向性,在锂离子嵌入和脱出的过程中,会产生10%左右的体积膨胀和收缩,其层状结构在循环过程中易被破坏。另外在循环过程中难免会有电解质溶剂共嵌于石墨层间,会产生气体和体积膨胀,致使石墨片层剥落,造成活性物质不可逆损失以及固体电解质界面膜(SEI膜)的不断被破坏和重生,消耗锂离子,从而导致电池循环寿命缩短。金属离子化合物有很好的导锂离子的性能,但是具有导电性较差的缺点,而且伴随着锂离子的嵌入和脱出存在较大的体积变化,因此其电化学性能、循环稳定性、倍率性并不理想。
因此如果能将碳材料和金属离子化合物锂离子导体复合在一起制备出新型容量高、倍率性能优异、寿命长的锂离子电池的负极材料,将对提高锂离子电池的性能产生促进作用。
发明内容
为解决上述问题,本发明提供了一种具有碳纤维结构的碳绑定的“锂离子导体-碳”复合负极材料及其制备方法,采用现场合成的具有碳纤维结构的高强度碳网结构将锂离子导体和碳负极材料绑定在一起制备出具有高功率密度的锂电池负极材料。
本发明提供了一种具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其包括以下步骤:
S1:将碳材料、锂离子导体、有机高分子材料和有机溶剂(可以溶解有机高分子材料)混合搅拌均匀后得到混合浆料A;
S2:将混合浆料A造粒干燥得到固体颗粒M;
S3:将固体颗粒M在惰性氛围中,经过高温碳化处理,得到具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料。
作为优选,步骤S1中所述碳材料选自石墨、软碳、硬碳中的至少一种。
作为优选,步骤S1中所述的锂离子导体是金属离子化合物。
作为优选,步骤S1中所述的锂离子导体中所含的金属离子是除Mn、Fe、Co、Ni、Cu、Au、Ag、Zn、Cd、Cr、Cd、Hg、Ge、Pb、Ru、Rh、Pd、Os、Ir、Pt等金属以外的其余金属的相应离子。
作为优选,步骤S1中所述的锂离子导体是选自导锂离子的金属氧化物、金属复合氧化物、金属硫化物、金属氮化物、金属氟化物、金属碳化物、金属硒化物、金属蹄(Te)化物、金属磷酸盐、Li2CO3、Li2TiO3、Li4Ti5O12、Li2ZrO3、LiVO3、Li3VO4、LiNbO3、Li3NbO4、
Li3Ln3M2O12(M=Te、W;Ln=Y、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm,Yb,Lu)中的至少一种。
作为优选,步骤S1中所述的锂离子导体中金属氮化物可以选自Li3N、Li3N-LiCl、Li9N2Cl、Li3AlN2、LiSi2N3、Li0.85Ca0.075Si2N中的至少一种。
作为优选,步骤S1中所述的锂离子导体中金属磷酸盐选自Li3PO4、LiMPO4(M是Mg2+、Ca2+、Sr2+、Ba2+中的致少一种)、LiM2(PO4)3(M=Ge、Ti、Hf)和Li1+xMxTi2-x(PO4)3(M=Al、Sc、Y、La)中的至少一种。
作为优选,步骤S1中所述锂离子导体与所述碳材料重量比选自1:2~1:100,优选自1:7~1:9。
作为优选,步骤S1中所述的有机高分子材料选自有机高分子材料中那些在经过高温碳化后可以转化为碳纤维的有机高分子材料。
作为优选,步骤S1中所述的有机高分子材料选自聚丙烯腈、酚醛树脂、沥青中的至少一种。
作为优选,步骤S1中所述的有机高分子材料的重量占不包括溶剂在内的其它物料总重量的百分比为1%~30%,优选为1.5%~10%。
作为优选,步骤S1中所述的有机溶剂是能溶解目标高分子材料的液体有机物,具体如:能溶解聚丙烯腈的有机溶剂选自二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)中的至少一种,但是不限于这几种溶剂,能溶解酚醛树脂的有机溶剂选自甲醇、乙醇、丙醇中至少一种,但是不限于这几种溶剂,以及能溶解沥青的有机溶剂选自液体烃类溶剂如汽油、柴油种的至少一种。
作为优选,步骤S3中所述碳化处理温度选自400-1500℃。
作为优选,步骤S3中所述碳化处理时间选自1-50h。
本发明的有益效果:
本发明方法制备具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料具有高强度的三维碳纤维网状结构,碳负极活性材料与锂离子导体材料的晶体被碳纤维网绑定在同一颗粒中,它有如下优点:
(1)本材料与相同颗粒尺寸的纯石墨碳负极材料相比较,具有更好的导锂离子性能;
(2)本发明方法制备的碳纤维绑定的锂离子导体-碳复合负极材料颗粒内部是由锂离子导体小晶体和碳负极活性材料小微粒经过碳纤维绑定形成,颗粒内部小晶体和碳小微粒之间的缝隙保证了电解质溶液可以充分地进入浸润,缩短了锂离子在碳小微粒中的扩散距离,提高了材料的高功率充放电电流密度;
(3)由于绑定锂离子导体小晶体和碳小微粒的是碳纤维,而碳纤维本身是导电的,所以材料也具有良好的导电性;
(4)可以容忍电池在充放电时材料的体积变化,颗粒内部锂离子导体小晶体和碳小微粒之间的缝隙可以缓冲体积变化;
(5)碳纤维有很高的抗拉强度和纤维柔软性两大特性,将锂离子导体和碳小微粒绑定后,在一定程度上缓冲或延缓了材料在充放电过程中发生的体积变化、粉化和团聚,还可以有效防止被绑定的碳小微粒在长期循环充放电条件下被剥离成多层石墨,从而提高了电极的循环稳定性。
(6)将锂离子导体-碳小微粒捆绑在一起包裹在三维碳纤维网内,更有利于锂离子导体和电解质界面的锂离子和电荷传输,继而提高材料的倍率性能。
(7)由于有些锂离子导体在碳负极材料和碳纤维网提供良好的导电性的条件下,也能提供较大的容量,所以有些复合材料的容量会比单独的碳负极材料容量更大。
本材料的生产工艺流程短,成本低,对制成的混合颗粒进行高温处理时,高分子材料被碳化成具有碳纤维结构的三维碳纤维网,把锂离子导体和碳小微粒捆绑在同一颗粒中,实现材料生产的一步完成。
附图说明
图1为实施例1纯中间相碳微球材料作为负极材料的倍率循环图。在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图2为实施例2制备的酚醛树脂制备碳纤维结构的碳绑定ZrO2/MgO-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、
500、600mA/g下进行。
图3为实施例2制备的酚醛树脂制备碳纤维结构的碳绑定ZrO2/MgO-碳复合负极材料的SEM照片。在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、
500、600mA/g下进行。
图4为实施例3制备的聚丙烯腈制备碳纤维结构的碳绑定ZrO2/CaO-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图5为实施例4制备的聚丙烯腈制备碳纤维结构的碳绑定TiO2/MgO/CaO-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图6为实施例5制备的酚醛树脂制备碳纤维结构的碳绑定TiO2/Li2O-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图7为实施例6制备的酚醛树脂制备碳纤维结构的碳绑定ZrO2/Y2O3-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、
500、600mA/g下进行。
图8为实施例7制备的酚醛树脂制备碳纤维结构的碳绑定TiO2/La2O3-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图9为实施例8制备的酚醛树脂制备碳纤维结构的碳绑定Li3PO4-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
具体实施方式
以下结合具体实施例及附图说明,对本发明的技术方案具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法进行进一步详细的说明。
实施例1
作为对比,本实施例用纯中间相碳微球材料制备半电池进行测试。
电池制作过程:称取0.8000g的中间相碳微球(N7),加入0.1003g的导电炭黑和
3.3333g的含3.0%PVDF的NMP溶液,使N7比导电炭黑比PVDF的质量比为8:1:1,球磨30min得浆料,把浆料涂在铜箔上,涂成厚度为90μm的极片,在120℃下在氮气氛的烘箱中烘3h,将极片在手套箱中制成半电池,先称取小圆片放在正极壳内,依次放入隔膜、60μL电解液、金属锂片、垫片、弹片和负极壳,在液压机上液压封装成纽扣电池。
电池测试过程:将上述纽扣电池,在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、500、600mA/g下进行,测定在不同电流密度下的克容量数据,得到说明书附图一的结果。
从说明书附图一中可以分析出,该实施例一中制备纯中间相碳微球材料测定结果表明在电流密度升高时,材料的克容量大幅度下降,在300mA/g时容量为150mAh/g;在400mA/g时容量为90mAh/g。
实施例2
本实施例是一种用酚醛树脂制备碳纤维结构的碳绑定ZrO2/MgO-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程:
(一)称取1324.00g无水乙醇,加入25.91g的ZrO2、16.94g的MgO和385.65g的中间相碳微球(平均粒度20μm),使金属氧化物/碳质量比为1:9,再加入64.27g的含20wt%的酚醛树脂的乙醇溶液,酚醛树脂占ZrO2、MgO、碳含量总量的3%,球磨混合后,出料得到混合浆料。
(二)在100℃下喷雾干燥,得到固体粉末。
(三)取上述固体粉末5.0012g在管式炉中,在N2下,在800℃烧制5h,得到酚醛树脂制备碳纤维结构的碳绑定ZrO2/MgO-碳复合负极材料。
电池制作过程:按质量比为94:3:3称取上述复合负极材料、导电炭黑、PVDF,加NMP使得固含量为24%,在真空搅拌机上搅拌20min后涂在铜箔表面,涂布厚度为120μm,在90℃鼓风干燥箱干燥30min,烘干后辊压切片,再放入真空干燥箱90℃烘12h。在手套箱中制成半电池,先称取小圆片放在正极壳内,依次放入隔膜、60μL电解液、金属锂片、垫片、弹片和负极壳,在液压机上液压封装成纽扣电池。
电池测试过程:将上述纽扣电池,以恒流充放电在33mA/g下循环1圈,再分别以100mA/g、200mA/g、300mA/g、400mA/g、500mA/g、600mA/g、700mA/g、800mA/g、900mA/g、1000mA/g的电流密度各循环10圈,最后再以100mA/g的电流密度循环10圈,得到如说明书附图2的结果。
从说明书附图2可知,在大电流密度下,该电池材料仍然可以保持比纯中间相碳材料大的容量(例一),并且具有很好的稳定性。从说明书附图3该负极材料的SEM图像可知,锂离子导体金属氧化物小晶体(ZrO2/MgO)和碳小微粒分散均匀,颗粒度小,起捆绑作用的碳纤维分布均匀,颗粒内部以及颗粒之间存在的间隙保证了电解质溶液可以充分进入浸润,缩短了锂离子在碳晶体中的扩散距离,保证了整个颗粒的稳定性。
实施例3
本实施例是一种用聚丙烯腈制备碳纤维结构的碳绑定ZrO2/CaO-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程:
(一)称取100.00g的水,加入21.54g的ZrO2和20.01g的CaCO3,使Zr:Ca的摩尔比为1:2,加入12.52g的聚乙烯醇(PEG),使PEG占ZrO2和CaCO3总量的30%,在球磨机
250r/min球磨10h,出料,加入120.0mL水冲洗,在120℃下喷雾干燥,得到白色的粉末。取白色粉末25.00g放在空气氛的管式炉中1000℃烧制7h,烧制后的样品粉碎过80目筛。
(二)称取6.96g上述烧制后的样品,加入10.0mL NMP和27.84g的碳(N7),使无机物/碳质量比为2:8,再加入34.8g的5wt.%的聚丙烯腈NMP溶液,聚丙烯腈占无机物、碳含量总量的5%,最后加入20.0mL的NMP,球磨后得到混合浆体。
(三)将混合浆体,在喷雾干燥器上150℃干燥,得到固体粉末。
(四)将固体粉末放入管式炉中,在N2氛围下1000℃烧制5h,得到用酚醛树脂制备碳纤维结构的碳绑定ZrO2/CaO-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同,结果如图4所示,材料具有优良的高电流密度性能,能在大电流密度下发挥出高容量。
实施例4
本实施例是一种用聚丙烯腈制备碳纤维结构的碳绑定TiO2/MgO/CaO-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程:
(一)称取100.00g的水,加入15.92g的TiO2、10.47g的MgO、5.642g的CaO、
9.61g的PEG,使PEG占TiO2、MgO、CaO总量的30%,球磨后,在120℃下喷雾干燥,得到白色的粉末。将25.07g的白色粉末放在空气氛的管式炉下1350℃烧制7h,烧制后的样品粉碎过80目筛。
(二)称取6.78g烧制后的上述样品,加入10.0mL NMP,球磨后加入12.59g的碳(N7),使无机物/碳质量比为3.5:6.5,再加入30.99g的5wt.%的聚丙烯腈NMP溶液,聚丙烯腈占无机物、碳含量总量的5%,最后加入30.0mL的NMP,球磨得到混合浆料。
(三)将混合浆料,喷雾干燥得到固体粉末。
(四)将上述固体粉末放入管式炉中,在N2氛围下900℃烧制5h,得到用聚丙烯腈制备碳纤维结构的碳绑定TiO2/MgO/CaO-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同,结果如图5所示,材料具有优良的高电流密度性能,能在大电流密度下发挥出高容量。
实施例5
本实施例是一种用酚醛树脂制备碳纤维结构的碳绑定TiO2/Li2O-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程:
(一)按摩尔比2:1分别称量2.0498g的LiOH·H2O和1.9509g的TiO2,然后称量6.0040g的片状石墨(HC-7)、30.99g的5wt.%的酚醛树脂的乙醇溶液和量取40.0ml的乙醇于球磨罐中,在180r/min下球磨6h后,出料,得到混合浆料。
(二)将混合浆料,喷雾干燥,得到固体粉末。
(三)将上述固体粉末放入高温管式炉中,在氩气气氛下,在850℃下保温4h,得用酚醛树脂制备碳纤维结构的碳绑定TiO2/Li2O-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同,结果如图6所示,材料具有优良的高电流密度性能,能在大电流密度下发挥出高容量。
实施例6
本实施例是一种用酚醛树脂制备碳纤维结构的碳绑定ZrO2/Y2O3-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程:
(一)称取1310.90g的无水乙醇、42.8559g的ZrO2、1.2856g的Y2O3搅拌5min,在砂磨机上以2500r/min转速砂磨15min,再加入397.22g的碳(FSN)、66.25g的20wt.%的酚醛树脂无水乙醇溶液,在2500r/min下砂磨10min,出料,得到混合浆料。
(二)将混合浆料在100℃下喷雾干燥,得到固体粉末。
(三)将上述固体粉末放入高温管式炉中,在N2气氛下下800℃烧制5h,得到用酚醛树脂制备碳纤维结构的碳绑定的ZrO2/Y2O3-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同,结果如图7所示,材料具有优良的高电流密度性能,能在大电流密度下发挥出高容量。
实施例7
本实施例是一种用酚醛树脂制备碳纤维结构的碳绑定TiO2/La2O3-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程:
(一)称取1335.06g的无水乙醇、42.8556g的TiO2、2.1436g的La2O3,搅拌5min,在砂磨机上在2500r/min下砂磨15min,再加入404.96g的碳(FSN)和67.56g的20wt.%的酚醛树脂无水乙醇溶液,球磨得混合浆料。
(二)将混合浆料,在喷雾干燥器上100℃干燥,得到黑色粉末。
(三)取上述6.8952g的黑色粉末放入高温管式炉中,在N2气氛下800℃烧制5h,得到用酚醛树脂制备碳纤维结构的碳绑定TiO2/La2O3-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同,结果如图8所示,材料具有优良的高电流密度性能,能在大电流密度下发挥出高容量。。
实施例8
本实施例是一种用酚醛树脂制备碳纤维结构的碳绑定Li3PO4-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程:
(一)称取900.05g的无水乙醇,加入30.06g的磷酸锂,搅拌5min,搅拌后在
2500r/min下砂磨15min,加入270.05g的碳(FSN),使磷酸锂/碳质量比为1:9,再加入45.06g的20wt.%的酚醛树脂,酚醛树脂占磷酸锂、碳含量总量的3%,2500r/min砂磨
10min,出料,得到混合浆料。
(二)将混合浆料,在100℃喷雾干燥器干燥,得到固体粉末。
(三)取上述固体粉末8.6043g放入高温管式炉中,在N2气氛下800℃烧制5h,得到用酚醛树脂制备碳纤维结构的碳绑定Li3PO4-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同,结果如图9所示,材料具有优良的高电流密度性能,能在大电流密度下发挥出高容量。
根据实施例1-8获得的负极材料,在电压范围为0.01V-2.00V,测试在电流密度分别为100、200、300、400、500、600mA/g下进行的倍率循环图,检测结果对比如表1所示。
表1
根据表1及说明书附图1-9所示数据,可以看出按照本发明方法制备的各种具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料在大电流密度下仍然保持了比纯碳材料高得多的容量,在高电流密度时,能保持高的克容量,并且具有很好的稳定性。与现有技术相比具有显著的进步。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。本领域技术人员根据本说明书公开的内容可以很容易地想到,可以根据实际需要对各实施例进行适当调整和重新组合,而不会脱离本申请的精神。本申请的保护范围以本申请的权利要求书为准。
Claims (16)
1.一种具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于:
该方法包括以下步骤:
S1:将碳材料、锂离子导体、有机高分子材料和有机溶剂混合搅拌均匀后得到混合浆料A;
S2:将混合浆料A造粒并且干燥得到固体颗粒M;
S3:将固体颗粒M在惰性氛围中,经过高温碳化处理,得到具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料;
其中,所述的锂离子导体是金属离子化合物,所述的金属离子化合物是除Mn、Fe、Co、Ni、Cu、Au、Ag、Zn、Cd、Cr、Cd、Hg、Ge、Pb、Ru、Rh、Pd、Os、Ir、Pt金属以外的其余金属相应的离子化合物;
或者,所述的锂离子导体是选自导锂离子的金属氧化物、金属复合氧化物、金属硫化物、金属氮化物、金属氟化物、金属碳化物、金属磷酸盐、金属硒化物、金属蹄化物、Li2CO3、Li2TiO3、Li4Ti5O12、Li2ZrO3、LiVO3、Li3VO4、LiNbO3、Li3NbO4、Li3Ln3M2O12中的至少一种,其中M是Te或W的一种,Ln是Y、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu中的一种。
2.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述碳材料选自石墨、软碳、硬碳中的至少一种。
3.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述金属氮化物选自Li3N、Li3N-LiCl、Li9N2Cl、Li3AlN2、LiSi2N3、Li0.85Ca0.075Si2N中的至少一种。
4.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述金属磷酸盐选自Li3PO4、LiMPO4、 LiN2(PO4)3或Li1+xQxTi2-x(PO4)3中的至少一种,其中M 是Mg2+、Ca2+、Sr2+或Ba2+中的一种,N是Ge、Ti或Hf中的一种,Q是Al、Sc、Y或La中的一种。
5.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S1中锂离子导体与所述碳材料重量比为1:2~1:100。
6.根据权利要求5所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S1中锂离子导体与所述碳材料重量比为1:7~1:9。
7.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S1中有机高分子材料是在碳化后可以转化为碳纤维的有机高分子材料。
8.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于:所述步骤S1中,有机高分子材料选自聚丙烯腈、酚醛树脂、沥青中的至少一种。
9.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S1中,有机高分子材料的重量占不包括溶剂在内的其它物料总重量的1%~30%。
10.根据权利要求9所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S1中,有机高分子材料的重量占不包括溶剂在内的其它物料总重量的2%~10%。
11.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S1中,有机溶剂选自能溶解目标高分子材料的液体物质。
12.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S1中,有机溶剂选自能溶解聚丙烯腈的有机溶剂二甲基甲酰胺(DMF)、N,N- 二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO) 中至少一种。
13.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S1中的有机溶剂选自能溶解酚醛树脂的有机溶剂甲醇、乙醇、丙醇中至少一种。
14.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S1中,有机溶剂选自能溶解沥青的有机溶剂选自液体烃类溶剂汽油、柴油中的至少一种。
15.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S3中,材料的碳化处理温度为400-1500℃。
16.根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法,其特征在于,所述步骤S3中,材料的碳化处理时间为1-50h。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811575295.XA CN111354925B (zh) | 2018-12-21 | 2018-12-21 | 具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的合成 |
KR1020217002478A KR20210022744A (ko) | 2018-12-21 | 2019-11-14 | 탄소 섬유 구조를 가진 탄소 결합 리튬 이온 도체-탄소 복합 캐소드 재료의 합성 |
JP2021504472A JP7070876B2 (ja) | 2018-12-21 | 2019-11-14 | 炭素繊維構造を有する炭素結合リチウムイオン導体-炭素複合負極材料の合成 |
US17/265,696 US20210384507A1 (en) | 2018-12-21 | 2019-11-14 | Carbon-bound lithium-ion conductor-carbon composite cathode material having carbon fiber structure and fabrication method therefor |
EP19898077.3A EP3832760A1 (en) | 2018-12-21 | 2019-11-14 | Carbon-bound lithium ion conductor-carbon composite cathode material having carbon fiber structure and fabrication method therefor |
PCT/CN2019/118250 WO2020125282A1 (zh) | 2018-12-21 | 2019-11-14 | 具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料及其制备方法。 |
KR1020237043638A KR20240001267A (ko) | 2018-12-21 | 2019-11-14 | 탄소 섬유 구조를 가진 탄소 결합 리튬 이온 도체-탄소 복합 캐소드 재료의 합성 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811575295.XA CN111354925B (zh) | 2018-12-21 | 2018-12-21 | 具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的合成 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111354925A CN111354925A (zh) | 2020-06-30 |
CN111354925B true CN111354925B (zh) | 2021-04-20 |
Family
ID=71100186
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811575295.XA Active CN111354925B (zh) | 2018-12-21 | 2018-12-21 | 具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的合成 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20210384507A1 (zh) |
EP (1) | EP3832760A1 (zh) |
JP (1) | JP7070876B2 (zh) |
KR (2) | KR20210022744A (zh) |
CN (1) | CN111354925B (zh) |
WO (1) | WO2020125282A1 (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113193199A (zh) * | 2021-04-30 | 2021-07-30 | 中国科学院宁波材料技术与工程研究所 | 一种石墨烯-锂离子导体材料复合导电浆料、其制备方法及应用 |
CN114094055A (zh) * | 2021-11-11 | 2022-02-25 | 杭州电子科技大学 | 一种磷化锂电极的制备方法 |
CN114242947A (zh) * | 2021-12-22 | 2022-03-25 | 杭州电子科技大学 | 一种碳包覆磷化锂电极及其制备方法 |
CN114275765A (zh) * | 2021-12-28 | 2022-04-05 | 杭州电子科技大学 | 一种磷化锂/碳纳米管@多孔碳核壳结构复合材料及其制备方法和应用 |
CN114256457B (zh) * | 2021-12-31 | 2023-12-05 | 国联汽车动力电池研究院有限责任公司 | 具有均质复合包覆层的富锂锰基正极材料及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104037405A (zh) * | 2013-03-06 | 2014-09-10 | 佛山市顺德宇红纳米科技有限公司 | 一种制备三氧化二铁/石墨烯/碳纤维复合材料的方法 |
CN106450253A (zh) * | 2016-10-25 | 2017-02-22 | 中国石油大学(华东) | 锂离子电池负极用高性能ZnO/沥青碳/碳纤维复合材料的制备方法 |
CN107293701A (zh) * | 2016-03-31 | 2017-10-24 | 比亚迪股份有限公司 | 一种锂离子电池负极活性材料及其制备方法、负极和包含该负极的锂离子电池 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09306476A (ja) * | 1996-05-13 | 1997-11-28 | Sony Corp | 非水電解液二次電池用負極材料およびこれを用いた非水電解液二次電池 |
KR100835883B1 (ko) * | 2006-07-14 | 2008-06-09 | 금호석유화학 주식회사 | 탄소나노섬유를 혼성화시킨 리튬이차전지용 음극 활물질 |
EP2781483B8 (en) | 2011-11-15 | 2018-10-17 | Denka Company Limited | Composite particles, method for producing same, electrode material for secondary batteries, and secondary battery |
CA2776205A1 (en) | 2012-05-08 | 2013-11-08 | Hydro-Quebec | Lithium-ion secondary battery and method of producing same |
KR20140121953A (ko) * | 2013-04-08 | 2014-10-17 | 주식회사 엘지화학 | 리튬 이차전지용 음극, 그 제조방법 및 이를 포함하는 리튬 이차 전지 |
CN105161725B (zh) * | 2015-08-12 | 2018-01-16 | 河南科技大学 | 一种锂离子动力电池用负极材料的制备方法 |
CN105428657A (zh) * | 2015-11-17 | 2016-03-23 | 天津市捷威动力工业有限公司 | 一种高能量密度快充型聚合物锂离子电池及其制备方法 |
US10454101B2 (en) * | 2017-01-25 | 2019-10-22 | StoreDot Ltd. | Composite anode material made of core-shell particles |
JP2018156867A (ja) | 2017-03-17 | 2018-10-04 | 株式会社豊田自動織機 | 負極材料の製造方法 |
-
2018
- 2018-12-21 CN CN201811575295.XA patent/CN111354925B/zh active Active
-
2019
- 2019-11-14 KR KR1020217002478A patent/KR20210022744A/ko active Application Filing
- 2019-11-14 WO PCT/CN2019/118250 patent/WO2020125282A1/zh unknown
- 2019-11-14 US US17/265,696 patent/US20210384507A1/en not_active Abandoned
- 2019-11-14 JP JP2021504472A patent/JP7070876B2/ja active Active
- 2019-11-14 EP EP19898077.3A patent/EP3832760A1/en active Pending
- 2019-11-14 KR KR1020237043638A patent/KR20240001267A/ko not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104037405A (zh) * | 2013-03-06 | 2014-09-10 | 佛山市顺德宇红纳米科技有限公司 | 一种制备三氧化二铁/石墨烯/碳纤维复合材料的方法 |
CN107293701A (zh) * | 2016-03-31 | 2017-10-24 | 比亚迪股份有限公司 | 一种锂离子电池负极活性材料及其制备方法、负极和包含该负极的锂离子电池 |
CN106450253A (zh) * | 2016-10-25 | 2017-02-22 | 中国石油大学(华东) | 锂离子电池负极用高性能ZnO/沥青碳/碳纤维复合材料的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN111354925A (zh) | 2020-06-30 |
KR20210022744A (ko) | 2021-03-03 |
US20210384507A1 (en) | 2021-12-09 |
EP3832760A1 (en) | 2021-06-09 |
JP2021532551A (ja) | 2021-11-25 |
WO2020125282A1 (zh) | 2020-06-25 |
JP7070876B2 (ja) | 2022-05-18 |
KR20240001267A (ko) | 2024-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111354925B (zh) | 具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的合成 | |
CN111987296B (zh) | 负极材料及使用其的电化学装置和电子装置 | |
KR102088491B1 (ko) | 리튬 이차전지용 음극활물질 및 이를 포함하는 리튬 이차전지용 음극 | |
KR100888685B1 (ko) | 코어-쉘형 리튬 이차전지용 음극 활물질 및 그 제조방법과이를 포함하는 리튬 이차전지 | |
KR101479320B1 (ko) | 리튬 이차 전지용 음극 활물질 및 이의 제조 방법 | |
US20190157712A1 (en) | High energy density secondary lithium batteries | |
KR20140140323A (ko) | 리튬 이차 전지용 음극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차전지 | |
CN108878892A (zh) | 正极极片及电池 | |
US20080044656A1 (en) | Carbonaceous composite particles and uses and preparation of the same | |
CN100515617C (zh) | 一种锂离子电池正极活性物质/碳复合材料的制备方法 | |
WO2018110263A1 (ja) | 複合黒鉛粒子、その製造方法及びその用途 | |
CN113228342A (zh) | 一种负极极片、包含该负极极片的电化学装置及电子装置 | |
JP2003173774A (ja) | リチウムイオン系二次電池用負極材およびその製造方法、および該負極材を用いたリチウムイオン系二次電池 | |
CN115425215A (zh) | 复合材料及其制备方法、电化学装置及电子装置 | |
CN102201564A (zh) | 非水电解质二次电池及非水电解质二次电池的制造方法 | |
CN105845886A (zh) | 一种离子电池负极材料及其制备方法 | |
CN111162254A (zh) | 硅碳复合负极材料的制备方法 | |
CN114937758B (zh) | 一种负极活性材料及含有该负极活性材料的负极片和电池 | |
CN113991074B (zh) | 一种超低温锰酸锂电池 | |
CN113594456B (zh) | 正极浆料及其制备方法、正极片和锂离子电池 | |
US20220002160A1 (en) | Composite graphite material and method for preparation thereof, secondary battery, and apparatus | |
JP2005174630A (ja) | 高出力型非水電解質二次電池 | |
CN115249799A (zh) | 钠离子电池松香基氮掺杂包覆硬碳负极材料及其制备方法 | |
JP2002015726A (ja) | ゲル電解質二次電池 | |
CN114585589A (zh) | 人造石墨、制备人造石墨的方法、包含所述人造石墨的负极、以及锂二次电池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |