CN106848219A - A kind of composite cathode material of lithium ion battery and preparation method thereof - Google Patents
A kind of composite cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN106848219A CN106848219A CN201710028228.5A CN201710028228A CN106848219A CN 106848219 A CN106848219 A CN 106848219A CN 201710028228 A CN201710028228 A CN 201710028228A CN 106848219 A CN106848219 A CN 106848219A
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- tin
- ion battery
- nitrogen
- lithium ion
- cathode material
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- 239000002131 composite material Substances 0.000 title claims abstract description 72
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 50
- 239000010406 cathode material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 69
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 67
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002135 nanosheet Substances 0.000 claims abstract description 15
- 238000005275 alloying Methods 0.000 claims abstract description 10
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 54
- 150000003606 tin compounds Chemical class 0.000 claims description 54
- 239000007787 solid Substances 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 47
- 239000002243 precursor Substances 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002096 quantum dot Substances 0.000 claims description 13
- 229930006000 Sucrose Natural products 0.000 claims description 11
- 239000005720 sucrose Substances 0.000 claims description 11
- 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 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical compound [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- -1 dicyanodiamine Chemical compound 0.000 claims description 2
- 238000006471 dimerization reaction Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000002902 organometallic compounds Chemical group 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims 2
- 229910052737 gold Inorganic materials 0.000 claims 2
- 229910052763 palladium Inorganic materials 0.000 claims 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 125000000185 sucrose group Chemical group 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 43
- 239000000956 alloy Substances 0.000 abstract description 14
- 229910045601 alloy Inorganic materials 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 238000000137 annealing Methods 0.000 abstract description 3
- 239000008188 pellet Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 56
- 150000001875 compounds Chemical class 0.000 description 26
- 238000012360 testing method Methods 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229910000990 Ni alloy Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000004513 sizing Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910000914 Mn alloy Inorganic materials 0.000 description 6
- 239000007767 bonding agent Substances 0.000 description 6
- NTIGMHLFJNXNBT-UHFFFAOYSA-N manganese tin Chemical compound [Mn].[Sn] NTIGMHLFJNXNBT-UHFFFAOYSA-N 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000010957 pewter Substances 0.000 description 6
- 229910000498 pewter Inorganic materials 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006253 efflorescence Methods 0.000 description 4
- 206010037844 rash Diseases 0.000 description 4
- 239000002733 tin-carbon composite material Substances 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000010974 bronze Substances 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001941 electron spectroscopy Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- JCLOGSKIMBJQAA-UHFFFAOYSA-N [Mo].[Sn] Chemical compound [Mo].[Sn] JCLOGSKIMBJQAA-UHFFFAOYSA-N 0.000 description 1
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a kind of composite cathode material of lithium ion battery and preparation method thereof, this lithium cell negative pole composite is made up of metallic tin or its alloy and nitrogenous carbon material.The tin or tin alloy/carbon composite are prepared by two steps annealing method.The particle size of metallic tin is smaller in composite, tin and its alloying pellet can be uniformly distributed on nitrogenous carbon nanosheet, nitrogenous carbon nanosheet is capable of the electrochemical properties of stable metal tin and its alloying pellet simultaneously, and this composite has cycle performance and larger specific capacity more long.The preparation process is simple of the composite, with low cost, it is easy to large-scale industrial production simultaneously.
Description
Technical field
High-performance lithium cell negative pole material and preparation method thereof is prepared the present invention relates to a kind of two steps annealing method.The lithium is electric first
Composite has specific capacity big, good cycling stability, high rate performance advantage high.Next preparation process is simple, can high-volume
Prepare.The invention belongs to inorganic functional material preparation field.
Background technology
Since twentieth century, lithium ion battery has obtained development at full speed.In mobile device, space flight and aviation, biological medicine,
Great popularization and application have been obtained in the fields such as public transport.At present, the negative material of the lithium ion battery of commercialization is mainly
Graphite, because graphite has cycle efficieny and cycle life higher, while having the advantages that relatively low discharge potential.But with
Social progress and the development of science and technology, the relatively low theoretical specific capacity of graphite (372mAh/g) seriously limits lithium battery
Performance, it is impossible to meet demand of the people to high-capacity battery.Therefore, seek a kind of negative material of high-energy-density turn into work as
The focus of preceding research.
The features such as metallic tin is with its theoretical specific capacity higher (996mAh/g), high magnification, high security, causes people
Extensive research, such as Solid State Ionics (2000,133,189-194) report tin tellurium alloy and do lithium cell negative pole material
Performance, Advanced Materials (2007,19,1632-1625) report nickeltin nano-array and do lithium cell negative pole
The performance of material.Although tin has specific capacity higher as lithium cell negative pole material, its volume in charge and discharge process becomes
Change is larger, causes electrode easily efflorescence to be failed, so as to shorten the life-span of lithium ion battery.In order to improve following for metal tin material
Ring stability, lifts battery life, and the method that various countries researcher proposes many mainly has：Nanosizing, using nano particle
Dimensional effect, reduces the invertibity that efflorescence improves charge and discharge process.Such as Journal of Power Sources (2009,188,
The nanometer tin for 578-582) reporting the load of copper nano-array does the performance of lithium cell negative pole.Alloying, including active metal with it is non-
Active metal is combined, and using the difference of the lithiumation current potential between different activities metal, matrix expands come buffer volumes each other, such as
Scientific Reports (2016,6,29356) report the performance that silicon stannum alloy does lithium cell negative pole material.Journal of
Electronic Materials (2016,45,3220-3226) report the performance that tin molybdenum alloy does lithium cell negative pole material.
Journal of Solid State Electrochemistry (2016,6,1743-1751) reports metallic tin and iron, cobalt
Alloy material Deng metal does lithium cell negative pole.Carbon composite, using the high resiliency and stability buffer metal lithiumation mistake of material
Volumetric expansion in journey, the cycle life of raising negative material, such as Journal of Chemistry Material (2009,
19,8378-8384) report metallic tin and do lithium cell negative pole with graphene composite material.International Journal of
Electrochemical Science (2016,11,3591-3603) are reported and prepared containing tin carbon nanometer with electrospinning process
Fiber does lithium cell negative pole, but the preparation technology and chemical property of these reports have much room for improvement at present.
The content of the invention
One purpose of the present invention is the nano composite material for proposing a kind of metallic tin and its alloy and high nitrogen content carbon, is solved
Stanniferous amount is low in existing lithium electric material, the defect that capacity is low or cycle life is poor, prepares a kind of stanniferous amount higher while circulation
Life-span preferable lithium cell negative pole composite.
The mentality of designing for being used for composite cathode material of lithium ion battery in the present invention is carried out sufficiently by predecessor
Mixing, lithium cell negative pole composite is prepared using the synergy between metal ion and organic matter by two steps annealing method.
The particle size of tin and its alloy is smaller in this composite, can be uniformly distributed on carbon nanosheet, while carbon nanosheet
And inert metal can alleviate the efflorescence that tin Volume Changes in charge and discharge process are brought.So that electrode material have it is fabulous
Chemical property.
Another object of the present invention is to provide a kind of process is simple, reproducible, with low cost, environment-friendly
The preparation method of tin and its alloy/carbon composite.The material has preparation process is simple, height ratio capacity, high stability, high power
The characteristics of rate performance.
Technical scheme is as follows：
A kind of composite cathode material of lithium ion battery, described composite cathode material of lithium ion battery (900) is including stanniferous
Quantum dot and nitrogenous carbon nanosheet, described stanniferous quantum dot are evenly distributed on nitrogenous carbon nanosheet, described stanniferous quantum
The quality of point accounts for the 50~80% of composite gross mass.
Described stanniferous quantum dot is tin quantum dot or tin alloy quantum dot；
Alloying element in addition to tin is selected from one or more in following element：Co,Fe,Mn,Ni,Si,Cu,Cr,Ti,
Zn,Al,Pb,Sb,In,Ge,Ag,Au,Pd,Pt,C；
Described nitrogenous carbon nanosheet has super-thin sheet-shaped pattern.
The preparation method of described composite cathode material of lithium ion battery is as follows：
By will not be after nitrogen-containing precursor (300), (500) three kinds of raw materials of nitrogen-containing precursor (400) and tin compound mix
Carry out two-step method calcining and obtain composite cathode material of lithium ion battery (900)；
Or by will not nitrogen-containing precursor (300), nitrogen-containing precursor (400), tin compound (500) and non-tin metal chemical combination
Two-step method calcining is carried out after (600) four kinds of raw material mixing of thing obtain composite cathode material of lithium ion battery (900).
Described not nitrogen-containing precursor (300) is 1 with the weight ratio of nitrogen-containing precursor (400)：(5-10)；
Described not nitrogen-containing precursor (300) is 1 with the weight ratio of tin compound (500)：(0.25-1)；
Such as contain non-tin compound (600), described tin compound (500) and non-tin compound (600) weight
Amount is than being (5-15)：1.
Described not nitrogen-containing precursor (300) is selected from one or two in sucrose, glucose.
Described nitrogen-containing precursor (400) is selected from urea, cyanamide, dicyanodiamine, cyanamid dimerization, melamine
Plant or several.
Described tin compound (500) is selected from the one kind in stannous chloride, tin oxalate, stannous oxalate, tin acetate, nitric acid tin
Or it is several.
Described non-tin compound (600) be the organo-metallic compound of the alloying element in addition to tin, nitrate,
Halide, oxalates or acetate, the described alloying element in addition to tin include one or more in following element：Co,
Fe,Mn,Ni,Si,Cu,Cr,Ti,Zn,Al,Pb,Sb,In,Ge,Ag,Au,Pd,Pt,C。
The preparation method of described composite cathode material of lithium ion battery, comprises the following steps：
1) mixed liquor (200) of configuration absolute ethyl alcohol and deionized water, adds not nitrogen-containing precursor (300), nitrogenous forerunner
Thing (400) and tin compound (500), or add not nitrogen-containing precursor (300), nitrogen-containing precursor (400), tin compound (500)
With non-tin compound (600), stir, obtain mixed solution (700), in mixed liquor (200) absolute ethyl alcohol and go from
The volume ratio of sub- water is 3~6:10；
2) by step 1) mixed solution (700) that obtains heated in being put into air dry oven, makes solvent abundant
Evaporation, obtains solid powder, and the heating-up temperature of air dry oven is 50~90 DEG C, and the heat time is 2~12 hours；
3) by step 2) solid powder that obtains is positioned in closed container to be placed in Muffle furnace and carries out at first step calcining
Reason, obtains solid powder (800), and first step calcining heat is 350~600 DEG C, and first step calcination time is 0.5~4 hour；
4) by step 3) solid powder (800) that obtains is placed in tube furnace, second step carried out under atmosphere of inert gases and is forged
Burning treatment, treatment temperature is 600~900 DEG C, obtains solid powder, i.e. composite cathode material of lithium ion battery (900), second step
Calcination time is 4~8 hours.
Described not nitrogen-containing precursor (300) is sucrose, and described nitrogen-containing precursor (400) is urea, described tin
Compound (500) is stannous chloride.
Final scheme is：Sucrose and urea are carried out into mixed dissolution in the mixed liquor of sucrose and water, is added in solution
Enter protochloride pink salt and other inert metal salt, be stirred until being completely dissolved.Solution is put into baking oven after heat drying,
The container that solid powder is put into sealing is placed in the treatment of Muffle furnace high temperature.The sample after high-temperature process is finally placed in tube furnace
In carry out heating reduction treatment, obtain lithium cell negative pole material.
Obtained tin of the invention and its alloy/carbon composite prepare lithium cell negative pole：By tin and its alloy/carbon negative pole material
Mixed with conductive black and binding agent PVDF, dropwise addition solvent (1-METHYLPYRROLIDONE) stirring is mixed to form and is homogenized
Material.Slurry is coated on Copper Foil to carry out dry sliced, is to be prepared into button cell to electrode to test with lithium metal.
Beneficial effects of the present invention：The method of first passage secondary clacining of the present invention is prepared extra small nano particle and is attached to
Carbon nanosheet surface, forms nano composite material, and the pattern of tin and its alloy is in nano particle in the composite, and I greatly
Control, can prepare the lithium ion battery with specific discharge capacity higher, excellent high rate performance and long circulation life.It is relatively existing
Technology, the technology of the present invention has the following advantages that：
1st, the preparation method of tin and its alloy/anode composite is simple easily into by the synthesis of two step calcination methods, repetition
Property it is good, it is with low cost, be adapted to industrial mass production.
2nd, the size of tin and alloy nanoparticle is controllable, and can be evenly distributed on carbon nanosheet surface.It is simultaneously nano level
Tin and alloy can slow down the efflorescence that volumetric expansion brings using nanometer size effect, again can sufficient lithiumation, with higher
Specific capacity.
3rd, the carbon nanosheet prepared with not nitrogen-containing precursor and nitrogen-containing precursor has graphitization state higher so that
Carbon nanosheet has larger specific surface area, electrical conductivity higher so that combination electrode has excellent high rate performance.
4th, carbon nanosheet and inert metal can alleviate volumetric expansion of the metallic tin in charge and discharge process, so that effectively
Improve the cycle life of combination electrode.
Brief description of the drawings
Fig. 1 is the preparation technology schematic diagram of tin of the invention and its compound lithium cell negative pole of alloy/carbon；
Fig. 2 is the scanning electron microscope diagram to the compound lithium cell negative pole material of tin/carbon in embodiment 1；
Fig. 3 is the transmission electron microscope figure to the compound lithium cell negative pole material of tin/carbon in embodiment 1；
Fig. 4 is the XRD diffracting spectrums to the compound lithium cell negative pole material of tin/carbon in embodiment 1；
Fig. 5 is to carry out 2A/g constant current charge-discharge tests to the compound lithium cell negative pole material of tin/carbon in embodiment 1, in 0.01V
Charging and discharging curve data under to 3.0V voltage windows；
Fig. 6 is to carry out 2A/g constant current charge-discharge tests to the compound lithium cell negative pole material of tin/carbon in embodiment 1, in 0.01V
Cycle life data under to 3.0V voltage windows；
Fig. 7 be carry out 0.5 to the compound lithium cell negative pole material of tin/carbon in embodiment 1,1,2,5,10A/g constant current multiplying powers fill
Discharge test, the loop-around data under 0.01V to 3.0V voltage windows；
Fig. 8 is the thermogravimetric analysis to the tin/carbon composite in embodiment 2；
Fig. 9 is to carry out 2A/g constant current charge-discharge tests to the compound lithium cell negative pole material of tin/carbon in embodiment 2, in 0.01V
Cycle life data under to 3.0V voltage windows；
Figure 10 is to carry out 2A/g constant current charge-discharge tests to the compound lithium cell negative pole material of tin/carbon in embodiment 3,
Cycle life data under 0.01V to 3.0V voltage windows；
Figure 11 is the thermogravimetric analysis to the tin/carbon composite in embodiment 3；
Figure 12 is the tem study to tin manganese alloy/carbon composite in embodiment 4；
Figure 13 is the power spectrum elementary analysis to tin manganese alloy/carbon composite in embodiment 4；
Figure 14 is to carry out 0.5A/g constant current charge-discharge surveys to the compound lithium cell negative pole material of tin manganese alloy/carbon in embodiment 4
Examination, the cycle life data under 0.01V to 3.0V voltage windows；
Figure 15 is the tem study to tin pewter/carbon composite in embodiment 5；
Figure 16 is the electron spectroscopy analysis to the nitrogen of tin pewter/carbon composite in embodiment 5；
Figure 17 is to carry out 0.5A/g constant current charge-discharge surveys to the compound lithium cell negative pole material of tin pewter/carbon in embodiment 5
Examination, the cycle life data under 0.01V to 3.0V voltage windows；
Figure 18 is the power spectrum elementary analysis to signal bronze/carbon composite in embodiment 6；
Figure 19 is to carry out 0.5A/g constant current charge-discharge surveys to the compound lithium cell negative pole material of signal bronze/carbon in embodiment 6
Examination, the cycle life data under 0.01V to 3.0V voltage windows；
Figure 20 is the power spectrum elementary analysis to tin-nickel alloy/carbon composite in embodiment 7；
Figure 21 is the thermogravimetric analysis to tin-nickel alloy/carbon composite in embodiment 7；
Figure 22 is to carry out 0.5A/g constant current charge-discharge surveys to the compound lithium cell negative pole material of tin-nickel alloy/carbon in embodiment 7
Examination, the cycle life data under 0.01V to 3.0V voltage windows；
Wherein, 100 is beaker, and 200 is mixed liquor, and 300 is not nitrogen-containing precursor, and 400 is nitrogen-containing precursor, and 500 is tin
Compound, 600 is non-tin compound, and 700 is mixed solution, and 800 is solid powder, and 900 is multiple for lithium ion battery negative
Condensation material.
Specific embodiment
Following examples are intended to be described in further detail present invention；And the protection of claim of the invention
Scope is not limited by the example.
Absolute ethyl alcohol in embodiment 1-7, purchased from Nanjing Chemistry Reagent Co., Ltd.；
Deionized water in embodiment 1-7, is the self-control of UNIQUE-R10 pure water meters；
Reagent in embodiment 1-7, purchased from Nanjing Chemistry Reagent Co., Ltd.；
Battery diaphragm in embodiment 1-7, purchased from Celgard companies, article No. is Celgard 2400；
The electrolyte in full battery in embodiment 1-7：1M LiPF6It is 1 to be dissolved in volume ratio:1 ethylene carbonate and
Diethyl carbonate.Purchased from Hefei Ke Jing Materials Technology Ltd..
Embodiment 1
The preparation method of the composite cathode material of lithium ion battery of the present embodiment, comprises the following steps：
1) 10 ml deionized waters are measured with graduated cylinder and 6 milliliters of ethanol are made into mixed liquor (200) addition beaker (100),
1 gram of sucrose (i.e. not nitrogen-containing precursor 300) and 10 grams of urea (i.e. nitrogen-containing precursor 400) is added afterwards, is eventually adding 1
Gram stannous chloride (i.e. tin compound 500) stir 2 hours, until solution is well mixed, obtain mixed solution (700).
2) mixed solution obtained in step 1 (700) is put into air dry oven to heat, heating-up temperature is 70 DEG C, plus
The hot time is 2.5 hours, obtains solid powder.
3) solid powder obtained in step 2 is put into closed container, being put into Muffle furnace carries out first step calcination processing,
Solid powder (800) is obtained, first step calcining heat is 550 DEG C, and first step calcination time is 1 hour.
4) solid powder obtained in step 3 (800) is put into tube furnace carries out second step calcining in argon hydrogen gaseous mixture
Treatment, second step calcining heat is 800 DEG C, and second step calcination time is 6 hours, obtains solid powder, as lithium ion battery
Anode material (900).
5) solid powder obtained in step 4 is ground, is mixed with conductive black and binding agent PVDF, be added dropwise
Organic solvent (1-METHYLPYRROLIDONE) stirring is mixed to form uniform sizing material.Slurry is coated on Copper Foil carry out it is dry sliced,
It is to be prepared into button cell to electrode to test with lithium metal.
Fig. 2 is the scanning electron microscope diagram of the compound lithium cell negative pole material of tin/carbon.As can be seen from the figure tin is without obvious
Aggregation nucleation and growth process, be combined with carbon well.
Fig. 3 is the transmission electron microscope figure of the compound lithium cell negative pole material of tin/carbon.It can be found that metallic tin from transmission plot
It is extra small nano particle, only several nanometers, while tin is distributed very uniformly on carbon nanosheet, density is also very big.
Fig. 4 is that x-ray diffractometer carries out continuous scanning in the range of 10~80 ° to the compound lithium cell negative pole material of tin/carbon
XRD diffracting spectrums.As can be seen from the figure composite material exhibits have gone out the feature of metallic tin and graphitized carbon complex spike, show multiple
Compound is metallic tin and carbon.
Fig. 5 is to carry out 2A/g constant current charge-discharge tests to the compound lithium cell negative pole material of tin/carbon in embodiment 1, in 0.01V
Charging and discharging curve data under to 3.0V voltage windows.Due to the nanometer size effect of tin, curve plateau is not it is obvious that made
Standby negative material is obtained in that the specific capacity of 684.8mAh/g.
Fig. 6 is to carry out 2A/g constant current charge-discharge tests to the compound lithium cell negative pole material of tin/carbon in embodiment 1, in 0.01V
Cycle life data under to 3.0V voltage windows.Electrode material circulates 1000 circle successors under the current density of 2A/g so to be had
The specific capacity of 518.4mAh/g, conservation rate reaches 75.7%.
Fig. 7 be carry out 0.5 to the compound lithium cell negative pole material of tin/carbon in embodiment 1,1,2,5,10A/g constant current multiplying powers fill
Discharge test, the loop-around data under 0.01V to 3.0V voltage windows.When the charging and discharging currents of electrode material are raised to from 0.5A/g
10A/g is former the specific capacity of 420.4mAh/g, and conservation rate is about 50%.
Embodiment 2
The preparation method of the composite cathode material of lithium ion battery of the present embodiment, comprises the following steps：
1) 10 ml deionized waters are measured with graduated cylinder and 3 milliliters of ethanol are made into mixed liquor (200) addition beaker (100),
1 gram of sucrose (i.e. not nitrogen-containing precursor 300) and 8 grams of melamine (i.e. nitrogen-containing precursor 400) is added afterwards, is finally added
The stannous acetate (i.e. tin compound 500) for entering 0.25 gram is stirred 3 hours, until solution is well mixed, obtains mixed solution
(700)。
2) mixed solution obtained in step 1 (700) is put into air dry oven to heat, heating-up temperature is 50 DEG C, plus
The hot time is 12 hours.
3) solid powder obtained in step 2 is put into closed container, being put into Muffle furnace carries out first step calcination processing,
Solid powder (800) is obtained, first step calcining heat is 600 DEG C, and first step calcination time is 0.5 hour.
4) solid powder obtained in step 3 (800) is put into tube furnace is carried out at second step calcining in argon atmosphere
Reason, obtains solid powder, i.e. composite cathode material of lithium ion battery (900), and second step calcining heat is 900 DEG C, and second step is forged
The burning time is 4 hours.
5) composite cathode material of lithium ion battery obtained in step 4 (900) is ground, with conductive black and bonding
Agent PVDF is mixed, and organic solvent (1-METHYLPYRROLIDONE) stirring is added dropwise and is mixed to form uniform sizing material.Slurry is coated on
Carry out dry sliced on Copper Foil, be to be prepared into button cell to electrode to test with lithium metal.
Fig. 8 be to the analysis of the stanniferous amount of the tin/carbon composite in embodiment 2, by thermogravimetric analysis can determine that containing
50% tin.
Fig. 9 is to carry out 2A/g constant current charge-discharge tests to the compound lithium cell negative pole material of tin/carbon in embodiment 2, in 0.01V
Cycle life data under to 3.0V voltage windows.Electrode material circulates 100 circle successors under the current density of 2A/g so to be had
The specific capacity of 530.6mAh/g.
Embodiment 3
The preparation method of the composite cathode material of lithium ion battery of the present embodiment, comprises the following steps：
1) 10 ml deionized waters are measured with graduated cylinder and 5 milliliters of ethanol are made into mixed liquor (200) addition beaker (100),
The glucose (i.e. not nitrogen-containing precursor 300) and 6 grams of dicyanodiamine (i.e. nitrogen-containing precursor 400) of 1 gram of addition afterwards, finally
Add 1 gram of stannous oxalate (i.e. tin compound 500) to stir 1 hour, until solution is well mixed, obtain mixed solution (700).
2) mixed solution obtained in step 1 (700) is put into air dry oven to heat, heating-up temperature is 90 DEG C, plus
The hot time is 2 hours.
3) solid powder obtained in step 2 is put into closed container, being put into Muffle furnace carries out first step calcination processing,
Solid powder (800) is obtained, first step calcining heat is 350 DEG C, and first step calcination time is 4 hours.
4) solid powder obtained in step 3 (800) is put into tube furnace carries out second step calcining under argon hydrogen gaseous mixture
Treatment, second step calcining heat is 600 DEG C, and second step calcination time is 8 hours, obtains solid powder, as lithium ion battery
Anode material (900).
5) composite cathode material of lithium ion battery obtained in step 4 (900) is ground, with conductive black and bonding
Agent PVDF is mixed, and organic solvent (1-METHYLPYRROLIDONE) stirring is added dropwise and is mixed to form uniform sizing material.Slurry is coated on
Carry out dry sliced on Copper Foil, be to be prepared into button cell to electrode to test with lithium metal.
Figure 10 is to carry out 2A/g constant current charge-discharge tests to the compound lithium cell negative pole material of tin/carbon in embodiment 3,
Cycle life data under 0.01V to 3.0V voltage windows.Electrode material only has after the circle of circulation 100 under the current density of 2A/g
The specific capacity of 425.9mAh/g, with 94% capability retention.
Figure 11 is the thermogravimetric analysis to the tin/carbon composite in embodiment 3.As can be seen from the figure tin in composite
Content 80%.
Embodiment 4
The preparation method of the composite cathode material of lithium ion battery of the present embodiment, comprises the following steps：
1) 10 ml deionized waters are measured with graduated cylinder and 6 milliliters of ethanol are made into mixed liquor (200) addition beaker (100),
1 gram of sucrose (i.e. not nitrogen-containing precursor 300) and 8 grams of melamine (i.e. nitrogen-containing precursor 400) is added afterwards, is finally added
Enter 0.75 gram of stannous chloride (i.e. tin compound 500) and 0.05 gram of manganese acetate (i.e. non-tin compound 600) stirring
1.5 hours, until solution is well mixed, obtain mixed solution (700).
2) mixed solution obtained in step 1 (700) is put into air dry oven to heat, heating-up temperature is 75 DEG C, plus
The hot time is 5 hours, obtains solid powder.
3) solid powder obtained in step 2 is put into closed container, being put into Muffle furnace carries out first step calcination processing,
First step calcining heat is 550 DEG C, and first step calcination time is 1.5 hours, obtains solid powder (800).
4) solid powder obtained in step 3 is put into tube furnace carries out second step calcination processing under nitrogen atmosphere, the
Two step calcining heats are 800 DEG C, and second step calcination time is 6 hours, obtain solid powder, and as lithium ion battery negative is combined
Material (900).
5) composite cathode material of lithium ion battery obtained in step 4 (900) is ground, with conductive black and bonding
Agent PVDF is mixed, and organic solvent (1-METHYLPYRROLIDONE) stirring is added dropwise and is mixed to form uniform sizing material.Slurry is coated on
Carry out dry sliced on Copper Foil, be to be prepared into button cell to electrode to test with lithium metal.
Figure 12 is the tem study to tin manganese alloy/carbon composite in embodiment 4, shows alloying pellet
In quantum dot rank.
Figure 13 is the elementary analysis being combined to tin manganese alloy/carbon in embodiment 4, shows to contain tin and manganese.
Figure 14 is to carry out 0.5A/g constant current charge-discharge surveys to the compound lithium cell negative pole material of tin manganese alloy/carbon in embodiment 4
Examination, the cycle life data under 0.01V to 3.0V voltage windows.Electrode material circulates 100 under the current density of 0.5A/g
Circle successor so has the specific capacity of 435.2mAh/g, with 90.3% capability retention.
Embodiment 5
The preparation method of the composite cathode material of lithium ion battery of the present embodiment, comprises the following steps：
1) 10 ml deionized waters are measured with graduated cylinder and 6 milliliters of ethanol are made into mixed liquor (200) addition beaker (100),
1 gram of sucrose (i.e. not nitrogen-containing precursor 300) and 10 grams of urea (i.e. nitrogen-containing precursor 400) is added afterwards, is eventually adding
0.75 gram of stannous chloride (i.e. tin compound 500) and 0.15 gram of antimony chloride (i.e. non-tin compound 600) stirring 2 are small
When, until solution is well mixed, obtain mixed solution (700).
2) mixed solution obtained in step 1 (700) is put into air dry oven to heat, heating-up temperature is 80 DEG C, plus
The hot time is 8 hours, obtains solid powder.
3) solid powder obtained in step 2 is put into closed container, being put into Muffle furnace carries out first step calcination processing,
Solid powder (800) is obtained, first step calcining heat is 500 DEG C, and first step calcination time is 1.5 hours, obtains solid powder
(800)。
4) solid powder obtained in step 3 (800) is put into tube furnace is carried out at second step calcining under argon atmosphere
Reason, second step calcining heat is 800 DEG C, and second step calcination time is 7 hours, obtains solid powder, and as lithium ion battery is born
Pole composite (900).
5) composite cathode material of lithium ion battery obtained in step 4 (900) is ground, with conductive black and bonding
Agent PVDF is mixed, and organic solvent (1-METHYLPYRROLIDONE) stirring is added dropwise and is mixed to form uniform sizing material.Slurry is coated on
Carry out dry sliced on Copper Foil, be to be prepared into button cell to electrode to test with lithium metal.
Figure 15 is the tem study to tin pewter/carbon composite in embodiment 5, shows what is prepared
Alloy is in quantum dot rank.
Figure 16 is the electron spectroscopy analysis to the nitrogen of tin pewter/carbon composite in embodiment 5, if show plus
The carbon of N doping is prepared by entering nitrogenous carbon source.
Figure 17 is to carry out 0.5A/g constant current charge-discharge surveys to the compound lithium cell negative pole material of tin pewter/carbon in embodiment 5
Examination, the cycle life data under 0.01V to 3.0V voltage windows.Electrode material circulates 50 circles under the current density of 0.5A/g
Successor so has the specific capacity of 521.4mAh/g.
Embodiment 6
The preparation method of the composite cathode material of lithium ion battery of the present embodiment, comprises the following steps：
1) 10 ml deionized waters are measured with graduated cylinder and 6 milliliters of ethanol are made into mixed liquor (200) addition beaker (100),
2 grams of glucose (i.e. not nitrogen-containing precursor 300) and 10 grams of urea (i.e. nitrogen-containing precursor 400) is added afterwards, is finally added
Stannous chloride (i.e. tin compound 500) and 0.1 gram of copper chloride (the i.e. non-tin compound 600) stirring 2 for entering 0.6 gram are small
When, until solution is well mixed, obtain mixed solution (700).
2) mixed solution obtained in step 1 (700) is put into air dry oven to heat, heating-up temperature is 60 DEG C, plus
The hot time is 12 hours, obtains solid powder.
3) solid powder obtained in step 2 is put into closed container, being put into Muffle furnace carries out first step calcination processing,
First step calcining heat is 400 DEG C, and first step calcination time is 4 hours, obtains solid powder (800).
4) be put into solid powder obtained in step 3 (800) carries out second step and forges in tube furnace under argon hydrogen mixed atmosphere
Burning treatment, second step calcining heat is 800 DEG C, and second step calcination time is 6 hours, obtains solid powder, as lithium-ion electric
Pond anode material (900).
5) composite cathode material of lithium ion battery obtained in step 4 (900) is ground, with conductive black and bonding
Agent PVDF is mixed, and organic solvent (1-METHYLPYRROLIDONE) stirring is added dropwise and is mixed to form uniform sizing material.Slurry is coated on
Carry out dry sliced on Copper Foil, be to be prepared into button cell to electrode to test with lithium metal.
Figure 18 is the elementary analysis being combined to gun-metal/carbon in embodiment 6, shows to contain tin and copper.
Figure 19 is to carry out 0.5A/g constant current charge-discharge surveys to the compound lithium cell negative pole material of signal bronze/carbon in embodiment 6
Examination, the cycle life data under 0.01V to 3.0V voltage windows.Electrode material circulates 100 under the current density of 0.5A/g
Circle successor so has the specific capacity of 530.6mAh/g.
Embodiment 7
The preparation method of the composite cathode material of lithium ion battery of the present embodiment, comprises the following steps：
1) 10 ml deionized waters are measured with graduated cylinder and 6 milliliters of ethanol are made into mixed liquor (200) addition beaker (100),
1 gram of sucrose (i.e. not nitrogen-containing precursor 300) and 10 grams of urea (i.e. nitrogen-containing precursor 400) is added afterwards, is eventually adding
0.5 gram of stannous chloride (i.e. tin compound 500) and 0.05 gram of nickel acetate (i.e. non-tin compound 600) stirring 2 are small
When, until solution is well mixed (700).
2) mixed solution obtained in step 1 (700) is put into air dry oven to heat, heating-up temperature is 70 DEG C, plus
The hot time is 5 hours, obtains solid powder.
3) solid powder obtained in step 2 is put into closed container, being put into Muffle furnace carries out first step calcination processing,
First step calcining heat is 550 DEG C, and first step calcination time is 1 hour, obtains solid powder (800).
4) solid powder obtained in step 3 (800) is put into tube furnace is carried out at second step calcining under argon atmosphere
Reason, second step calcining heat is 750 DEG C, and second step calcination time is 8 hours, obtains solid powder, and as lithium ion battery is born
Pole composite (900).
5) composite cathode material of lithium ion battery obtained in step 4 (900) is ground, with conductive black and bonding
Agent PVDF is mixed, and organic solvent (1-METHYLPYRROLIDONE) stirring is added dropwise and is mixed to form uniform sizing material.Slurry is coated on
Carry out dry sliced on Copper Foil, be to be prepared into button cell to electrode to test with lithium metal.
Figure 20 is the elementary analysis being combined to tin-nickel alloy/carbon in embodiment 7, shows to contain tin and nickel.
Figure 21 is the thermogravimetric analysis to the tin-nickel alloy/carbon composite in embodiment 7.As can be seen from the figure composite wood
The content of tin-nickel alloy is 60.5% in material.
Figure 22 is to carry out 0.5A/g constant current charge-discharge surveys to the compound lithium cell negative pole material of tin-nickel alloy/carbon in embodiment 7
Examination, the cycle life data under 0.01V to 3.0V voltage windows.Electrode material circulates 100 under the current density of 0.5A/g
Circle successor so has the specific capacity of 530.6mAh/g.
Claims (10)
1. a kind of composite cathode material of lithium ion battery, it is characterised in that described composite cathode material of lithium ion battery（900）
Including stanniferous quantum dot and nitrogenous carbon nanosheet, described stanniferous quantum dot is evenly distributed on nitrogenous carbon nanosheet, described
The quality of stanniferous quantum dot accounts for the 50~80% of composite gross mass.
2. composite cathode material of lithium ion battery according to claim 1, it is characterised in that：
Described stanniferous quantum dot is tin quantum dot or tin alloy quantum dot；
Alloying element in addition to tin is selected from one or more in following element：Co, Fe, Mn, Ni, Si, Cu, Cr,
Ti, Zn, Al, Pb, Sb, In, Ge, Ag, Au, Pd, Pt, C。
3. the preparation method of composite cathode material of lithium ion battery as claimed in claim 1 or 2, it is characterised in that preparation side
Method is as follows：
By will not nitrogen-containing precursor（300）, nitrogen-containing precursor（400）And tin compound（500）Carried out after three kinds of raw material mixing
Two-step method calcining obtains composite cathode material of lithium ion battery（900）；
Or by will not nitrogen-containing precursor（300）, nitrogen-containing precursor（400）, tin compound（500）With non-tin compound
（600）Two-step method calcining is carried out after four kinds of raw material mixing obtain composite cathode material of lithium ion battery（900）.
4. the preparation method of composite cathode material of lithium ion battery according to claim 3, it is characterised in that
Described not nitrogen-containing precursor（300）With nitrogen-containing precursor（400）Weight ratio be 1：（5-10）；
Described not nitrogen-containing precursor（300）With tin compound（500）Weight ratio be 1：（0.25-1）；
Such as contain non-tin compound（600）, described tin compound（500）With non-tin compound（600）Weight ratio
For（5-15）：1.
5. the preparation method of composite cathode material of lithium ion battery according to claim 3, it is characterised in that it is described not
Nitrogen-containing precursor（300）Selected from one or two in sucrose, glucose.
6. the preparation method of composite cathode material of lithium ion battery according to claim 3, it is characterised in that described contains
Nitrogen predecessor（400）Selected from one or more in urea, cyanamide, dicyanodiamine, cyanamid dimerization, melamine.
7. the preparation method of composite cathode material of lithium ion battery according to claim 3, it is characterised in that described tin
Compound（500）Selected from one or more in stannous chloride, tin oxalate, stannous oxalate, tin acetate, nitric acid tin.
8. the preparation method of composite cathode material of lithium ion battery according to claim 3, it is characterised in that described
Non- tin compound（600）It is organo-metallic compound, nitrate, halide, the oxalates of the alloying element in addition to tin
Or acetate, the described alloying element in addition to tin includes one or more in following element：Co, Fe, Mn, Ni,
Si, Cu, Cr, Ti, Zn, Al, Pb, Sb, In, Ge, Ag, Au, Pd, Pt, C。
9. the preparation method of composite cathode material of lithium ion battery according to claim 3, it is characterised in that including as follows
Step：
1）The mixed liquor of configuration absolute ethyl alcohol and deionized water（200）, add not nitrogen-containing precursor（300）, nitrogen-containing precursor
（400）And tin compound（500）, or add not nitrogen-containing precursor（300）, nitrogen-containing precursor（400）, tin compound（500）With
Non- tin compound（600）, stir, obtain mixed solution（700）, mixed liquor（200）Middle absolute ethyl alcohol and deionization
The volume ratio of water is 3~6:10；
2）By step 1) mixed solution that obtains（700）It is put into air dry oven and is heated, solvent is fully evaporated,
Solid powder is obtained, the heating-up temperature of air dry oven is 50~90 DEG C, and the heat time is 2~12 hours；
3）By step 2）The solid powder for obtaining is positioned in closed container to be placed in carries out first step calcination processing in Muffle furnace, obtain
To solid powder（800）, first step calcining heat is 350~600 DEG C, and first step calcination time is 0.5~4 hour；
4）By step 3）The solid powder for obtaining（800）It is placed in tube furnace, is carried out at second step calcining under atmosphere of inert gases
Reason, treatment temperature is 600~900 DEG C, obtains solid powder, i.e. composite cathode material of lithium ion battery（900）, second step calcining
Time is 4~8 hours.
10. the preparation method of composite cathode material of lithium ion battery according to claim 9, it is characterised in that described
Not nitrogen-containing precursor（300）It is sucrose, described nitrogen-containing precursor（400）It is urea, described tin compound（500）It is chlorination
Stannous.
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Cited By (5)
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| CN108199029A (en) * | 2018-01-11 | 2018-06-22 | 电子科技大学 | A kind of silkworm excrement mixes tin iron cell negative material and preparation method thereof |
| CN108400343A (en) * | 2018-02-13 | 2018-08-14 | 山东大学 | A kind of nitrogen load carbon nanosheet lithium oxygen battery anode catalytic agent material and preparation method thereof that high-performance cobalt granule is modified |
| CN109148845A (en) * | 2018-08-07 | 2019-01-04 | 欣旺达电子股份有限公司 | The nitrogen-doped carbon negative electrode material and preparation method thereof of nanometer tin modification |
| CN111313026A (en) * | 2020-02-26 | 2020-06-19 | 扬州大学 | Porous nitrogen-doped carbon/amorphous antimony compound, preparation method and application |
| CN116169288A (en) * | 2023-03-09 | 2023-05-26 | 湖南钠能时代科技发展有限公司 | Metal quantum dot/hard carbon negative electrode material and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108199029A (en) * | 2018-01-11 | 2018-06-22 | 电子科技大学 | A kind of silkworm excrement mixes tin iron cell negative material and preparation method thereof |
| CN108400343A (en) * | 2018-02-13 | 2018-08-14 | 山东大学 | A kind of nitrogen load carbon nanosheet lithium oxygen battery anode catalytic agent material and preparation method thereof that high-performance cobalt granule is modified |
| CN109148845A (en) * | 2018-08-07 | 2019-01-04 | 欣旺达电子股份有限公司 | The nitrogen-doped carbon negative electrode material and preparation method thereof of nanometer tin modification |
| CN109148845B (en) * | 2018-08-07 | 2021-03-02 | 欣旺达电子股份有限公司 | Nano-tin-modified nitrogen-doped carbon negative electrode material and preparation method thereof |
| CN111313026A (en) * | 2020-02-26 | 2020-06-19 | 扬州大学 | Porous nitrogen-doped carbon/amorphous antimony compound, preparation method and application |
| CN111313026B (en) * | 2020-02-26 | 2022-07-05 | 扬州大学 | Porous nitrogen-doped carbon/amorphous antimony compound, preparation method and application |
| CN116169288A (en) * | 2023-03-09 | 2023-05-26 | 湖南钠能时代科技发展有限公司 | Metal quantum dot/hard carbon negative electrode material and preparation method thereof |
| CN116169288B (en) * | 2023-03-09 | 2024-03-05 | 湖南钠能时代科技发展有限公司 | Metal quantum dot/hard carbon negative electrode material and preparation method thereof |
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