WO2023155540A1 - Dealloyed sodium ion battery negative electrode material and preparation method therefor - Google Patents
Dealloyed sodium ion battery negative electrode material and preparation method therefor Download PDFInfo
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- WO2023155540A1 WO2023155540A1 PCT/CN2022/135886 CN2022135886W WO2023155540A1 WO 2023155540 A1 WO2023155540 A1 WO 2023155540A1 CN 2022135886 W CN2022135886 W CN 2022135886W WO 2023155540 A1 WO2023155540 A1 WO 2023155540A1
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 33
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 83
- 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 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 17
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052745 lead Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 238000009713 electroplating Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000956 alloy Substances 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 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 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 12
- 239000001119 stannous chloride Substances 0.000 claims description 12
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
- 229920000620 organic polymer Polymers 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 229910021385 hard carbon Inorganic materials 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 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 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052789 astatine Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229930182830 galactose Natural products 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 238000009831 deintercalation Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 230000007935 neutral effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- -1 palladium ions Chemical class 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 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
- 150000002739 metals Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006913 SnSb Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- BSPSZRDIBCCYNN-UHFFFAOYSA-N phosphanylidynetin Chemical class [Sn]#P BSPSZRDIBCCYNN-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the application belongs to the technical field of sodium ion batteries, and in particular relates to a dealloyed sodium ion battery negative electrode material and a preparation method thereof.
- Lithium-ion batteries play an important role in energy storage modules for electric vehicles and handheld electronic devices.
- the application of lithium-ion batteries in the field of renewable energy power generation and energy storage in the future is limited due to limited lithium resources and high energy storage costs.
- Sodium-ion batteries have an electrochemical reaction principle similar to lithium-ion batteries, and sodium resources are abundant, widely distributed, and low in cost.
- sodium-ion batteries are expected to be applied in large-scale energy storage systems, and thus have attracted extensive attention from scientific research and industry.
- the large radius and heavy weight of sodium ions the kinetics of sodium ions in electrode materials is slow, which hinders the practical application of sodium ion batteries. difficulty.
- Graphite is the most mature anode material for lithium-ion batteries. It has been confirmed that when graphite is used as the negative electrode of a sodium ion battery, sodium ions can only intercalate into graphite to generate an 8-stage NaC 64 compound in a carbonate electrolyte. In the past decade, anode materials for sodium-ion batteries have developed rapidly, and researchers have developed a series of hard carbons, heteroatom-doped carbon materials, intercalation compounds, conversion and alloyed anodes.
- high-capacity negative electrode materials are mainly concentrated in metal oxide/sulfide materials, alloy materials, etc.
- anode materials with an alloy mechanism have attracted the attention of researchers due to their higher specific capacity and better safety, such as tin-antimony alloys, tin-phosphorus compounds, and SnGeSb ternary alloys.
- the theoretical specific capacity of SnSb alloy is as high as 853mAh/g, which is a very potential negative electrode material for sodium-ion batteries, but its volume expansion during charging and discharging causes material pulverization, which leads to rapid degradation of battery performance, such as tin-based materials in alloy- The volume expansion rate reached 358% during the dealloying process.
- the present application aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present application proposes a negative electrode material for a dealloyed sodium ion battery and a preparation method thereof.
- a negative electrode material for dealloyed sodium-ion batteries which consists of solid carbon particles and nano-scale metal mesh coated on the surface of the solid carbon particles, or consists of nano-scale metal mesh and its interior
- the supported carbon skeleton is composed of a hollow or three-dimensional porous shape, and the composition of the nanoscale metal mesh is at least one of Sn, Pb, Bi, Ge or Sb.
- the particle size of the dealloyed sodium ion battery negative electrode material is 1-5 ⁇ m.
- the present application also provides a preparation method of the dealloyed sodium ion battery negative electrode material, comprising the following steps:
- S2 Add the carbon-containing particles with a metal palladium layer on the surface to the electroplating solution, and perform plating under stirring to obtain carbon-containing particles with an alloy coating;
- the electroplating solution contains Ni and Sn, Pb, Bi, At least one of Ge or Sb; plating under stirring can prevent particle agglomeration.
- step S3 Introduce carbon monoxide to the carbon-containing particles with an alloy coating, and then soak in the first organic solvent to obtain de-alloyed particles; when the carbon-containing particles are organic polymers, proceed to step S4; When the carbon-containing particles are hard carbon, the dealloyed particles obtained in this step are finished products;
- the carbon-containing particles are subjected to the following pretreatment: adding the carbon-containing particles to a sodium hydroxide solution for heating, washing with water, and then adding to a nitric acid solution for heating, Wash again with water.
- the purpose of adding sodium hydroxide solution for treatment is to remove surface dirt, preferably, the concentration of the sodium hydroxide solution is 5-30%, heated to boiling, and boiled for 15-30min; the purpose of treatment with nitric acid solution is to corrode carbon-containing Particle surface, enhance its ability to combine with the coating, preferably, the concentration of nitric acid solution is 15-25%, heated to boiling, boiled for 15-25min.
- step S1 the solid-to-liquid ratios of the sodium hydroxide solution and the nitric acid solution treatment process are both 20-30 g/L.
- step S1 the particle size of the carbon-containing particles is ⁇ 5 ⁇ m.
- the concentration of hydrochloric acid in the mixed solution of hydrochloric acid and stannous chloride is 1.5-2.0 mol/L, and the concentration of stannous chloride is 15-20 g/L.
- the purpose of treating with the mixed solution of hydrochloric acid and stannous chloride is to make the surface of the carbonaceous particles absorb a layer of easily oxidizable stannous ions.
- the boiling time of the mixed solution of hydrochloric acid and stannous chloride is 10-20min .
- the concentration of hydrochloric acid in the mixed solution of hydrochloric acid and palladium chloride is 1.5-2.0 mol/L, and the concentration of palladium chloride is 0.5-1 g/L.
- the purpose of treating with a mixed solution of hydrochloric acid and palladium chloride is to reduce palladium ions to active metal palladium and attach to the surface of carbon-containing particles.
- the boiling time of the mixed solution of hydrochloric acid and palladium chloride is 10-20min.
- the concentration of the sodium hypophosphite solution is 30-50g/L, and the soaking time of the sodium hypophosphite solution is 10-20min.
- the purpose of soaking with sodium hypophosphite solution is to remove tin and palladium ions on the surface of carbon-containing particles.
- step S1 the solid-to-liquid ratio of the mixed solution of hydrochloric acid and stannous chloride, the mixed solution of hydrochloric acid and palladium chloride, and the sodium hypophosphite solution treatment process are all 40-60g/ L.
- the organic polymer is at least one of polystyrene, polyacetylene, polyaniline, polypyrrole or polythiophene.
- step S2 after the plating is completed, solid-liquid separation is performed, and the obtained solid is first washed with deionized water, and then washed with absolute ethanol.
- step S2 the plating time is 5-10 minutes.
- the first organic solvent is at least one of benzene, acetone, ether, tetrachlorinated naphthalene, ethanol, chloroform or carbon tetrachloride.
- step S3 the pressure of the carbon monoxide is ⁇ 0.1 MPa, the treatment temperature is 38-93° C., and the treatment time is 0.5-1.0 h.
- the second organic solvent is a good solvent, preferably at least one of tetrahydrofuran, dichloromethane or chloroform.
- the carbon source solution is at least one of solutions of glucose, starch, sucrose, fructose, lactose or galactose; the concentration of the carbon source solution is 0.05-2g /mL.
- step S4 the solid-to-liquid ratio of the hydrothermal reaction is 1g:(1-10)mL; the temperature of the hydrothermal reaction is 150-200°C, and the reaction time is 2 -5h.
- step S4 the carbonization temperature is 200-550° C., and the carbonization time is 1-12 hours.
- carbon-containing particles are firstly subjected to pre-plating treatment to obtain a catalytically active metal palladium layer on the surface, which is easy to attach to metal particles during subsequent electroplating, and then an electroplating solution containing nickel is used for alloy electroplating to make the target metal (Sn , Pb, Bi, Ge or Sb) and nickel are co-deposited on the surface of carbon-containing particles, and after dealloying treatment, nickel and carbon monoxide react to form nickel carbonyl, which is dissolved in an organic solvent to remove nickel, thereby forming on the surface of carbon-containing particles
- Nano-scale metal mesh when used as a negative electrode material, its internal nano-porous structure can not only buffer the volume change brought by the charging and discharging process, but also increase the contact area between the electrode and the electrolyte, with high capacity, excellent Cycle and rate performance, while the metal produced by electroplating has high density and mechanical strength, and can well resist the problems caused by its volume expansion when it is used as a negative electrode material for
- Carbon-containing particles can be carbonized when organic polymers are selected, so that a supportive three-dimensional porous carbon skeleton structure is formed inside the particles.
- Carbon-containing particles can also choose wire Type organic polymer, after the metal mesh is prepared, the linear organic polymer inside the particle is removed with an organic solvent, and then carbonized after soaking in a carbon source solution, so that a supporting hollow carbon skeleton structure is formed inside the metal mesh.
- the combination of metal mesh and carbon materials can improve the strength and conductivity of particles, and the three-dimensional porous or hollow carbon skeleton structure can further increase the specific surface area of the material, which is more conducive to the deintercalation of sodium ions. When used as anode materials for sodium-ion batteries, it can Further improve cycle performance and specific capacity.
- FIG. 1 is a SEM image of the dealloyed sodium ion battery negative electrode material prepared in Example 1 of the present application.
- a negative electrode material for a dealloyed sodium ion battery is prepared. Its structure is composed of solid carbon particles and nano-scale metal mesh coated on the surface of the solid carbon particles, with a particle size of 1-5 ⁇ m.
- the preparation process is as follows:
- Pre-plating treatment Select hard carbon with a particle size of ⁇ 5 ⁇ m, add it to 20% sodium hydroxide solution, boil for 20 minutes (to remove surface dirt), wash with deionized water until neutral, and then add 20% nitric acid In the solution, boil for 20 minutes (erode the surface of the particles and enhance their binding ability with the coating), wash with deionized water until neutral, and the solid-to-liquid ratio during the treatment process is 25g/L;
- step (2) Add the hard carbon treated in step (1) into HCl of 1.5mol/L and stannous chloride solution of 20g/L and boil for 15min (adsorb a layer of easily oxidizable stannous ions), wash with deionized water to neutrality, then added to 1.5mol/L HCl and 0.5g/L palladium chloride solution and boiled for 20min (palladium ions are reduced to active metal palladium attached to the particle surface), washed with deionized water until neutral, Then add to 50g/L sodium hypophosphite solution and soak for 20min (to remove tin and palladium ions on the particle surface), dry after solid-liquid separation, and the solid-liquid ratio of the treatment process is 50g/L;
- the composition of the alloy electroplating solution is 50g/L of SnCl 2 , 280g/L of NiCl 2 , 50g/L of (NH 4 )HF 2 , pH is 2-2.5, and current density is 1 -2A/dm 2 , the temperature is 60°C;
- a de-alloyed sodium-ion battery negative electrode material is prepared. Its structure is composed of a nanoscale metal mesh and a three-dimensional porous carbon skeleton supported inside, with a particle size of 1-5 ⁇ m.
- the preparation process is as follows:
- Pre-plating treatment select polystyrene with a particle size of ⁇ 5 ⁇ m, add it to 15% sodium hydroxide solution, boil for 15 minutes (to remove surface dirt), wash with deionized water until neutral, and then add 15% sodium hydroxide solution. Boil in nitric acid solution for 15 minutes (to erode the particle surface and enhance its binding ability with the coating), wash with deionized water until neutral, and the solid-to-liquid ratio during the treatment process is 20g/L;
- step (2) Add the polystyrene treated in step (1) to 2.0mol/L HCl and 15g/L stannous chloride solution and boil for 20min (adsorbing a layer of easily oxidizable stannous ions), deionized water Wash until neutral, then add to 1.5mol/L HCl and 1g/L palladium chloride solution and boil for 20min (palladium ions are reduced to active metal palladium attached to the particle surface), washed with deionized water until neutral, Then add to 30g/L sodium hypophosphite solution and soak for 10min (to remove tin and palladium ions on the particle surface), dry after solid-liquid separation, and the solid-liquid ratio of the treatment process is 40g/L;
- the composition of alloy electroplating solution is 45g/L of SnCl 2 , 285g/L of NiCl 2 , 55g/L of (NH 4 )HF 2 , pH is 2-2.5, current density 1 -2A/dm 2 , the temperature is 70°C;
- Carbonization treatment carbonize the dealloyed sodium particles obtained in step (5), and react in an inert atmosphere at 215° C. for 12 hours to obtain a dealloyed sodium ion battery negative electrode material.
- a de-alloyed sodium-ion battery negative electrode material is prepared. Its structure is composed of a nanoscale metal mesh and a hollow carbon skeleton supported inside it, with a particle size of 1-5 ⁇ m.
- the preparation process is as follows:
- Pre-plating treatment select polystyrene with particle size ⁇ 5 ⁇ m, add to 30% sodium hydroxide solution, boil for 30 minutes (to remove surface dirt), wash with deionized water until neutral, and then add to 25% sodium hydroxide solution In nitric acid solution, boil for 25min (to erode the surface of the particles and enhance their binding ability with the coating), wash with deionized water until neutral, and the solid-liquid ratio during the treatment process is 30g/L;
- step (2) Add the polystyrene treated in step (1) to 2.0mol/L HCl and 20g/L stannous chloride solution and boil for 20min (adsorbing a layer of easily oxidizable stannous ions), deionized water Wash until neutral, then add to 2.0mol/L HCl and 1g/L palladium chloride solution and boil for 20min (palladium ions are reduced to active metal palladium attached to the particle surface), washed with deionized water until neutral, Then add it to the sodium hypophosphite solution of 50g/L and soak for 20min (to remove tin and palladium ions on the particle surface), dry after solid-liquid separation, and the solid-liquid ratio in the treatment process is 60g/L;
- the composition of the alloy electroplating solution is 30g/L of PbCl 2 , 45g/L of NiCl 2 , 50g/L of NH 2 SO 3 H, 120g/L of HEDP, 10g/L of Hydrazine hydrochloride, pH 9-10, current density 0.5-1A/dm 2 , temperature 25°C;
- Electroplating Add the carbon-containing particles treated by S2 into the electroplating solution, perform plating under stirring, and electroplate for 8 minutes;
- Carbonization treatment soak the dealloyed particles in dichloromethane, remove the internal polystyrene, add them to 1g/mL starch solution, and carry out hydrothermal reaction.
- the solid-to-liquid ratio of the hydrothermal reaction is 1g: 2mL, the reaction temperature is 160°C, and the reaction time is 3h. After the reaction is completed, the solid is collected and then carbonized.
- the carbonization is carried out in an inert atmosphere at 215°C for 12h, and the dealloyed sodium ion battery negative electrode material is obtained.
- This comparative example prepares a kind of Sn/C composite material by carbothermal reduction method, and concrete process is:
- SnO2 and activated carbon powder with a material ratio of 1:3 in an agate mortar, mix well, put the mixture into a porcelain boat, place it in a tube furnace, and heat it at 5°C/min under the protection of argon. Raise the temperature to 950°C, keep it warm for 8h, and then naturally cool to room temperature to obtain the Sn/C composite material.
- the material is mainly composed of Sn spherical particles and block-shaped activated carbon.
- the Sn balls are uniformly dispersed and adsorbed on the block-shaped activated carbon.
- the size of the Sn spherical particles is about 0.5-7 ⁇ m.
Abstract
The present application discloses a dealloyed sodium ion battery negative electrode material and a preparation method therefor. The sodium ion battery negative electrode material is composed of solid carbon particles and a nanoscale metal mesh coated on the surface of the solid carbon particles, or is composed of a nanoscale metal mesh and a carbon skeleton supporting at the interior of said mesh, the carbon skeleton being hollow or three-dimensional porous, and the composition of the nanoscale metal mesh being at least one of Sn, Pb, Bi, Ge, or Sb. The combination of the metal mesh and the carbon material can improve the strength and conductivity of the particles; in addition, the three-dimensional porous or hollow carbon skeleton structure can further increase the specific surface area of the material, which is more conducive to the deintercalation of sodium ions and can improve cyclic performance and specific capacity.
Description
本申请属于钠离子电池技术领域，具体涉及一种去合金化钠离子电池负极材料及其制备方法。The application belongs to the technical field of sodium ion batteries, and in particular relates to a dealloyed sodium ion battery negative electrode material and a preparation method thereof.
锂离子电池在电动汽车和手持电子设备的储能模块中发挥了重要作用。然而，在未来可再生能源发电储能领域中的应用，锂离子电池却因为有限的锂资源和较高的储能成本而受到限制。钠离子电池具有和锂离子电池类似的电化学反应原理，且钠资源储量丰富、分布广泛、成本低廉。在锂离子电池的大规模发展可能受到锂资源短缺的瓶颈制约情况下，钠离子电池有望在规模储能***中得到应用，因而受到科研界和工业界的广泛关注。但是由于钠离子半径较大且质量较重，造成钠离子在电极材料中的动力学缓慢，使得钠离子电池实用化进程受阻，因此寻找合适的钠离子宿主负极材料比锂离子电池负极材料更为困难。Lithium-ion batteries play an important role in energy storage modules for electric vehicles and handheld electronic devices. However, the application of lithium-ion batteries in the field of renewable energy power generation and energy storage in the future is limited due to limited lithium resources and high energy storage costs. Sodium-ion batteries have an electrochemical reaction principle similar to lithium-ion batteries, and sodium resources are abundant, widely distributed, and low in cost. As the large-scale development of lithium-ion batteries may be restricted by the bottleneck of lithium resource shortage, sodium-ion batteries are expected to be applied in large-scale energy storage systems, and thus have attracted extensive attention from scientific research and industry. However, due to the large radius and heavy weight of sodium ions, the kinetics of sodium ions in electrode materials is slow, which hinders the practical application of sodium ion batteries. difficulty.
石墨是最成熟的锂离子电池负极材料。已有人证实石墨用作钠离子电池负极时，在碳酸酯类电解液中，钠离子只能嵌入石墨生成8阶的NaC
64化合物。近十年来，钠离子电池负极材料发展迅速，研究人员开发了一系列的硬炭、杂原子掺杂碳材料、插层化合物、转化和合金化负极。
Graphite is the most mature anode material for lithium-ion batteries. It has been confirmed that when graphite is used as the negative electrode of a sodium ion battery, sodium ions can only intercalate into graphite to generate an 8-stage NaC 64 compound in a carbonate electrolyte. In the past decade, anode materials for sodium-ion batteries have developed rapidly, and researchers have developed a series of hard carbons, heteroatom-doped carbon materials, intercalation compounds, conversion and alloyed anodes.
目前，高容量的负极材料主要集中于金属氧化物/硫化物材料、合金类材料等。其中，具有合金机制的负极材料因拥有较高的比容量和更好的安全性，而备受研究者的关注，例如锡锑合金、锡磷化合物和SnGeSb三元合金等。SnSb合金理论比容量高达853mAh/g，是一种非常有潜力的钠离子电池负极材料，但其在充放电过程中体积膨胀造成材料粉化进而导致电池性能迅速衰减，如锡基材料在合金-脱合金的过程中体积膨胀率达到了358％。At present, high-capacity negative electrode materials are mainly concentrated in metal oxide/sulfide materials, alloy materials, etc. Among them, anode materials with an alloy mechanism have attracted the attention of researchers due to their higher specific capacity and better safety, such as tin-antimony alloys, tin-phosphorus compounds, and SnGeSb ternary alloys. The theoretical specific capacity of SnSb alloy is as high as 853mAh/g, which is a very potential negative electrode material for sodium-ion batteries, but its volume expansion during charging and discharging causes material pulverization, which leads to rapid degradation of battery performance, such as tin-based materials in alloy- The volume expansion rate reached 358% during the dealloying process.
为了改善这些金属材料的循环性能，常采用的手段是电化学活性金属与电化学惰性的金属合金化。例如研究者采用Sn与Cu、Sb、Ag、Ni等元素合金化， 一定程度上改进了循环性能，但是收效不理想。在报道的研究中还采用过机械合金化法、化学沉淀法、固相烧结得复合氧化物法以及溅射镀膜法等，以上的制备方法都是为了得到微细的锡颗粒分散嵌布在惰性组分中来提高循环能力。但目前该类材料的循环性能还有待进一步提高。In order to improve the cycle performance of these metal materials, a common method is to alloy electrochemically active metals with electrochemically inert metals. For example, researchers used Sn to alloy elements such as Cu, Sb, Ag, and Ni, which improved cycle performance to a certain extent, but the effect was not satisfactory. In the reported research, mechanical alloying method, chemical precipitation method, solid-phase sintering to obtain composite oxide method, and sputtering coating method are also used. The above preparation methods are all for the purpose of obtaining fine tin particles dispersed in the inert group. points to improve the circulation capacity. However, the cycle performance of such materials still needs to be further improved.
发明内容Contents of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.
本申请旨在至少解决上述现有技术中存在的技术问题之一。为此，本申请提出一种去合金化钠离子电池负极材料及其制备方法。The present application aims to solve at least one of the technical problems in the above-mentioned prior art. For this reason, the present application proposes a negative electrode material for a dealloyed sodium ion battery and a preparation method thereof.
根据本申请的一个方面，提出了一种去合金化钠离子电池负极材料，由实心碳粒及包覆于所述实心碳粒表面的纳米级金属网组成，或由纳米级金属网及其内部支撑的碳骨架组成，所述碳骨架为空心状或三维多孔状，所述纳米级金属网的组成为Sn、Pb、Bi、Ge或Sb中的至少一种。According to one aspect of the present application, a negative electrode material for dealloyed sodium-ion batteries is proposed, which consists of solid carbon particles and nano-scale metal mesh coated on the surface of the solid carbon particles, or consists of nano-scale metal mesh and its interior The supported carbon skeleton is composed of a hollow or three-dimensional porous shape, and the composition of the nanoscale metal mesh is at least one of Sn, Pb, Bi, Ge or Sb.
在本申请的一些实施方式中，所述去合金化钠离子电池负极材料的粒径为1-5μm。In some embodiments of the present application, the particle size of the dealloyed sodium ion battery negative electrode material is 1-5 μm.
本申请还提供所述的去合金化钠离子电池负极材料的制备方法，包括以下步骤：The present application also provides a preparation method of the dealloyed sodium ion battery negative electrode material, comprising the following steps:
S1：将含碳颗粒加入到盐酸与氯化亚锡的混合溶液中煮沸一段时间，洗涤后加入到盐酸与氯化钯的混合溶液中煮沸一段时间，洗涤后再加入到次磷酸钠溶液中浸泡，固液分离，得到表面附有金属钯层的含碳颗粒；所述含碳颗粒为硬碳或有机聚合物；S1: Add the carbon-containing particles to the mixed solution of hydrochloric acid and stannous chloride and boil for a period of time. After washing, add them to the mixed solution of hydrochloric acid and palladium chloride and boil for a period of time. After washing, add them to the solution of sodium hypophosphite for soaking , solid-liquid separation to obtain carbon-containing particles with a metal palladium layer on the surface; the carbon-containing particles are hard carbon or organic polymers;
S2：将所述表面附有金属钯层的含碳颗粒加入到电镀液中，在搅拌下施镀，得到具有合金镀层的含碳颗粒；所述电镀液中含有Ni以及Sn、Pb、Bi、Ge或Sb中的至少一种；搅拌下施镀可以防止粒子团聚。S2: Add the carbon-containing particles with a metal palladium layer on the surface to the electroplating solution, and perform plating under stirring to obtain carbon-containing particles with an alloy coating; the electroplating solution contains Ni and Sn, Pb, Bi, At least one of Ge or Sb; plating under stirring can prevent particle agglomeration.
S3：向所述具有合金镀层的含碳颗粒通入一氧化碳处理，再加入到第一有机溶剂中浸泡，得到去合金化颗粒；当所述含碳颗粒为有机聚合物时，进行步 骤S4；当所述含碳颗粒为硬碳时，本步骤所得到的去合金化颗粒即为成品；S3: Introduce carbon monoxide to the carbon-containing particles with an alloy coating, and then soak in the first organic solvent to obtain de-alloyed particles; when the carbon-containing particles are organic polymers, proceed to step S4; When the carbon-containing particles are hard carbon, the dealloyed particles obtained in this step are finished products;
S4：选择以下任一种方法进行：(1)将所述去合金化颗粒在惰性气氛下进行碳化，即得；(2)将所述去合金化颗粒置于第二有机溶剂中浸泡，再置于碳源溶液中进行水热反应，然后在惰性气氛下进行碳化，即得；其中，方法(2)中使用的含碳颗粒为可溶性线型有机聚合物。用第二有机溶剂浸泡去合金化颗粒的目的是去除内部的含碳颗粒。方法(1)碳化后得到的颗粒其内部为三维多孔状的碳骨架，方法(2)碳化后得到的颗粒其内部为空心状的碳骨架，两种碳骨架都起到支撑纳米级金属网的作用。S4: Choose any of the following methods: (1) carbonize the dealloyed particles under an inert atmosphere; (2) soak the dealloyed particles in a second organic solvent, and then It is obtained by placing it in a carbon source solution for hydrothermal reaction, and then carbonizing it under an inert atmosphere; wherein, the carbon-containing particles used in the method (2) are soluble linear organic polymers. The purpose of soaking the dealloyed grains with the second organic solvent is to remove the inner carbonaceous grains. Method (1) The particle obtained after carbonization has a three-dimensional porous carbon skeleton inside, and the particle obtained after method (2) carbonization has a hollow carbon skeleton inside, and both carbon skeletons play a role in supporting the nanoscale metal mesh. effect.
在本申请的一些实施方式中，步骤S1中，所述含碳颗粒经过以下前处理：将所述含碳颗粒加入到氢氧化钠溶液中加热，用水洗涤后，再加入到硝酸溶液中加热，再用水洗涤。加入氢氧化钠溶液处理的目的是去除表面污物，优选的，所述氢氧化钠溶液的浓度为5-30％，加热至煮沸，煮沸15-30min；用硝酸溶液处理的目的是侵蚀含碳颗粒表面，增强其与镀层的结合能力，优选的，硝酸溶液的浓度为15-25％，加热至煮沸，煮沸15-25min。In some embodiments of the present application, in step S1, the carbon-containing particles are subjected to the following pretreatment: adding the carbon-containing particles to a sodium hydroxide solution for heating, washing with water, and then adding to a nitric acid solution for heating, Wash again with water. The purpose of adding sodium hydroxide solution for treatment is to remove surface dirt, preferably, the concentration of the sodium hydroxide solution is 5-30%, heated to boiling, and boiled for 15-30min; the purpose of treatment with nitric acid solution is to corrode carbon-containing Particle surface, enhance its ability to combine with the coating, preferably, the concentration of nitric acid solution is 15-25%, heated to boiling, boiled for 15-25min.
在本申请的一些优选的实施方式中，步骤S1中，所述氢氧化钠溶液与所述硝酸溶液处理过程的固液比均为20-30g/L。In some preferred embodiments of the present application, in step S1, the solid-to-liquid ratios of the sodium hydroxide solution and the nitric acid solution treatment process are both 20-30 g/L.
在本申请的一些实施方式中，步骤S1中，所述含碳颗粒的粒度≤5μm。In some embodiments of the present application, in step S1, the particle size of the carbon-containing particles is ≤5 μm.
在本申请的一些实施方式中，步骤S1中，所述盐酸与氯化亚锡的混合溶液中盐酸的浓度为1.5-2.0mol/L，氯化亚锡的浓度为15-20g/L。用盐酸与氯化亚锡的混合溶液处理的目的是使含碳颗粒表面吸附一层易氧化的亚锡离子，优选的，所述盐酸与氯化亚锡的混合溶液煮沸的时间为10-20min。In some embodiments of the present application, in step S1, the concentration of hydrochloric acid in the mixed solution of hydrochloric acid and stannous chloride is 1.5-2.0 mol/L, and the concentration of stannous chloride is 15-20 g/L. The purpose of treating with the mixed solution of hydrochloric acid and stannous chloride is to make the surface of the carbonaceous particles absorb a layer of easily oxidizable stannous ions. Preferably, the boiling time of the mixed solution of hydrochloric acid and stannous chloride is 10-20min .
在本申请的一些实施方式中，步骤S1中，所述盐酸与氯化钯的混合溶液中盐酸的浓度为1.5-2.0mol/L，氯化钯的浓度为0.5-1g/L。用盐酸与氯化钯的混合溶液处理的目的是使钯离子还原为具有活性的金属钯附在含碳颗粒表面。优选的，所述盐酸与氯化钯的混合溶液煮沸的时间为10-20min。In some embodiments of the present application, in step S1, the concentration of hydrochloric acid in the mixed solution of hydrochloric acid and palladium chloride is 1.5-2.0 mol/L, and the concentration of palladium chloride is 0.5-1 g/L. The purpose of treating with a mixed solution of hydrochloric acid and palladium chloride is to reduce palladium ions to active metal palladium and attach to the surface of carbon-containing particles. Preferably, the boiling time of the mixed solution of hydrochloric acid and palladium chloride is 10-20min.
在本申请的一些实施方式中，步骤S1中，所述次磷酸钠溶液的浓度为 30-50g/L，次磷酸钠溶液浸泡的时间为10-20min。用次磷酸钠溶液浸泡的目的是去除含碳颗粒表面的锡与钯离子。In some embodiments of the present application, in step S1, the concentration of the sodium hypophosphite solution is 30-50g/L, and the soaking time of the sodium hypophosphite solution is 10-20min. The purpose of soaking with sodium hypophosphite solution is to remove tin and palladium ions on the surface of carbon-containing particles.
在本申请的一些实施方式中，步骤S1中，所述盐酸与氯化亚锡的混合溶液、盐酸与氯化钯的混合溶液、次磷酸钠溶液处理过程的固液比均为40-60g/L。In some embodiments of the present application, in step S1, the solid-to-liquid ratio of the mixed solution of hydrochloric acid and stannous chloride, the mixed solution of hydrochloric acid and palladium chloride, and the sodium hypophosphite solution treatment process are all 40-60g/ L.
在本申请的一些实施方式中，步骤S1中，所述有机聚合物为聚苯乙烯、聚乙炔、聚苯胺、聚吡咯或聚噻吩中的至少一种。In some embodiments of the present application, in step S1, the organic polymer is at least one of polystyrene, polyacetylene, polyaniline, polypyrrole or polythiophene.
在本申请的一些实施方式中，步骤S2中，所述施镀完成后，进行固液分离，将所得固体先用去离子水洗涤，再采用无水乙醇洗涤。In some embodiments of the present application, in step S2, after the plating is completed, solid-liquid separation is performed, and the obtained solid is first washed with deionized water, and then washed with absolute ethanol.
在本申请的一些实施方式中，步骤S2中，所述施镀的时间为5-10min。In some embodiments of the present application, in step S2, the plating time is 5-10 minutes.
在本申请的一些实施方式中，步骤S3中，所述第一有机溶剂为苯、丙酮、***、四氯化萘、乙醇、三氯甲烷或四氯化碳中的至少一种。In some embodiments of the present application, in step S3, the first organic solvent is at least one of benzene, acetone, ether, tetrachlorinated naphthalene, ethanol, chloroform or carbon tetrachloride.
在本申请的一些实施方式中，步骤S3中，所述一氧化碳的压力≥0.1MPa，处理温度为38-93℃，处理的时间为0.5-1.0h。In some embodiments of the present application, in step S3, the pressure of the carbon monoxide is ≥0.1 MPa, the treatment temperature is 38-93° C., and the treatment time is 0.5-1.0 h.
在本申请的一些实施方式中，步骤S4中，所述第二有机溶剂为良溶剂，优选为四氢呋喃、二氯甲烷或氯仿中的至少一种。In some embodiments of the present application, in step S4, the second organic solvent is a good solvent, preferably at least one of tetrahydrofuran, dichloromethane or chloroform.
在本申请的一些实施方式中，步骤S4中，所述碳源溶液为葡萄糖、淀粉、蔗糖、果糖、乳糖或半乳糖的溶液中的至少一种；所述碳源溶液的浓度为0.05-2g/mL。In some embodiments of the present application, in step S4, the carbon source solution is at least one of solutions of glucose, starch, sucrose, fructose, lactose or galactose; the concentration of the carbon source solution is 0.05-2g /mL.
在本申请的一些实施方式中，步骤S4中，所述水热反应的固液比为1g:(1-10)mL；所述水热反应的温度为150-200℃，反应的时间为2-5h。In some embodiments of the present application, in step S4, the solid-to-liquid ratio of the hydrothermal reaction is 1g:(1-10)mL; the temperature of the hydrothermal reaction is 150-200°C, and the reaction time is 2 -5h.
在本申请的一些实施方式中，步骤S4中，所述碳化的温度为200-550℃，碳化的时间为1-12h。In some embodiments of the present application, in step S4, the carbonization temperature is 200-550° C., and the carbonization time is 1-12 hours.
根据本申请的一种优选的实施方式，至少具有以下有益效果：According to a preferred embodiment of the present application, it has at least the following beneficial effects:
1、本申请首先将含碳颗粒进行镀前处理，得到表层附有催化活性的金属钯层，易于后续电镀时金属粒子的附着，再采用含镍的电镀液进行合金电镀，使目标金属(Sn、Pb、Bi、Ge或Sb)与镍共同沉积到含碳颗粒表面，经去合金化 处理，使镍与一氧化碳反应生成羰基镍，经有机溶剂溶解从而脱除镍，从而在含碳颗粒表面形成纳米级的金属网，在作为负极材料使用时，其内部的纳米多孔结构既可以缓冲充放电过程中带来的体积变化又可以增大电极与电解液的接触面积，具有高的容量、优良的循环和倍率性能，同时电镀产生的金属具有较高的致密度和机械强度，在作为负极材料充放电时，能很好的阻抗其体积膨胀带来的问题。1. In the present application, carbon-containing particles are firstly subjected to pre-plating treatment to obtain a catalytically active metal palladium layer on the surface, which is easy to attach to metal particles during subsequent electroplating, and then an electroplating solution containing nickel is used for alloy electroplating to make the target metal (Sn , Pb, Bi, Ge or Sb) and nickel are co-deposited on the surface of carbon-containing particles, and after dealloying treatment, nickel and carbon monoxide react to form nickel carbonyl, which is dissolved in an organic solvent to remove nickel, thereby forming on the surface of carbon-containing particles Nano-scale metal mesh, when used as a negative electrode material, its internal nano-porous structure can not only buffer the volume change brought by the charging and discharging process, but also increase the contact area between the electrode and the electrolyte, with high capacity, excellent Cycle and rate performance, while the metal produced by electroplating has high density and mechanical strength, and can well resist the problems caused by its volume expansion when it is used as a negative electrode material for charging and discharging.
2、由于电镀金属具有不同的熔点，可选择性的进行碳化处理，含碳颗粒选择有机聚合物时可进行碳化，使颗粒内部形成支撑性的三维多孔碳骨架结构，含碳颗粒也可以选择线型有机聚合物，在制备完金属网后，用有机溶剂除去颗粒内部的线型有机聚合物，再浸泡碳源溶液后进行碳化，使得金属网内部形成支撑性的中空碳骨架结构。金属网与碳材料结合能够提升颗粒的强度和导电性，并且三维多孔或中空的碳骨架结构可进一步提升材料的比表面积，更加利于钠离子的脱嵌，作为钠离子电池负极材料使用时，可进一步提升循环性能和比容量。2. Since electroplated metals have different melting points, they can be selectively carbonized. Carbon-containing particles can be carbonized when organic polymers are selected, so that a supportive three-dimensional porous carbon skeleton structure is formed inside the particles. Carbon-containing particles can also choose wire Type organic polymer, after the metal mesh is prepared, the linear organic polymer inside the particle is removed with an organic solvent, and then carbonized after soaking in a carbon source solution, so that a supporting hollow carbon skeleton structure is formed inside the metal mesh. The combination of metal mesh and carbon materials can improve the strength and conductivity of particles, and the three-dimensional porous or hollow carbon skeleton structure can further increase the specific surface area of the material, which is more conducive to the deintercalation of sodium ions. When used as anode materials for sodium-ion batteries, it can Further improve cycle performance and specific capacity.
下面结合附图和实施例对本申请做进一步的说明，其中：Below in conjunction with accompanying drawing and embodiment the present application is described further, wherein:
图1为本申请实施例1制备的去合金化钠离子电池负极材料的SEM图。FIG. 1 is a SEM image of the dealloyed sodium ion battery negative electrode material prepared in Example 1 of the present application.
以下将结合实施例对本申请的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本申请的目的、特征和效果。显然，所描述的实施例只是本申请的一部分实施例，而不是全部实施例，基于本申请的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本申请保护的范围。The idea and technical effects of the present application will be clearly and completely described below in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present application. Apparently, the described embodiments are only some of the embodiments of the present application, not all of them. Based on the embodiments of the present application, other embodiments obtained by those skilled in the art without creative efforts belong to The protection scope of this application.
实施例1Example 1
本实施例制备了一种去合金化钠离子电池负极材料，其结构由实心碳粒及包覆于实心碳粒表面的纳米级金属网组成，粒径为1-5μm，其制备过程为：In this example, a negative electrode material for a dealloyed sodium ion battery is prepared. Its structure is composed of solid carbon particles and nano-scale metal mesh coated on the surface of the solid carbon particles, with a particle size of 1-5 μm. The preparation process is as follows:
(1)镀前处理：选用粒度≤5μm的硬碳，加入到20％的氢氧化钠溶液中，煮沸20min(去除表面污物)，去离子水洗涤至中性，再加入到20％的硝酸溶液中，煮沸20min(侵蚀颗粒表面，增强其与镀层的结合能力)，去离子水洗涤至中性，处理过程的固液比为25g/L；(1) Pre-plating treatment: Select hard carbon with a particle size of ≤5 μm, add it to 20% sodium hydroxide solution, boil for 20 minutes (to remove surface dirt), wash with deionized water until neutral, and then add 20% nitric acid In the solution, boil for 20 minutes (erode the surface of the particles and enhance their binding ability with the coating), wash with deionized water until neutral, and the solid-to-liquid ratio during the treatment process is 25g/L;
(2)将步骤(1)处理后的硬碳加入到1.5mol/L的HCl和20g/L的氯化亚锡溶液中煮沸15min(吸附一层易氧化的亚锡离子)，去离子水洗涤至中性，再加入到1.5mol/L的HCl和0.5g/L的氯化钯溶液中煮沸20min(钯离子还原为具有活性的金属钯附在颗粒表面)，去离子水洗涤至中性，再加入到50g/L的次磷酸钠溶液中浸泡20min(去除颗粒表面的锡与钯离子)，固液分离后干燥，处理过程的固液比均为50g/L；(2) Add the hard carbon treated in step (1) into HCl of 1.5mol/L and stannous chloride solution of 20g/L and boil for 15min (adsorb a layer of easily oxidizable stannous ions), wash with deionized water to neutrality, then added to 1.5mol/L HCl and 0.5g/L palladium chloride solution and boiled for 20min (palladium ions are reduced to active metal palladium attached to the particle surface), washed with deionized water until neutral, Then add to 50g/L sodium hypophosphite solution and soak for 20min (to remove tin and palladium ions on the particle surface), dry after solid-liquid separation, and the solid-liquid ratio of the treatment process is 50g/L;
(3)制备含镍合金电镀液：合金电镀液的成分为50g/L的SnCl
2、280g/L的NiCl
2、50g/L的(NH
4)HF
2，pH为2-2.5，电流密度1-2A/dm
2，温度为60℃；
(3) Preparation of nickel-containing alloy electroplating solution: the composition of the alloy electroplating solution is 50g/L of SnCl 2 , 280g/L of NiCl 2 , 50g/L of (NH 4 )HF 2 , pH is 2-2.5, and current density is 1 -2A/dm 2 , the temperature is 60°C;
(4)电镀：将步骤(2)处理好的硬碳加入到合金电镀液中，在搅拌下施镀，电镀8min；(4) Electroplating: Add the hard carbon processed in step (2) into the alloy electroplating solution, apply plating under stirring, and electroplate for 8 minutes;
(5)去合金化处理：电镀完成后，固液分离，先用去离子水洗涤固体，再采用无水乙醇洗涤，向得到的颗粒通入一氧化碳处理0.5h，一氧化碳的压力≥0.1MPa，处理温度为60℃，加入丙酮浸泡，固液分离后得到去合金化钠离子电池负极材料。(5) Dealloying treatment: After the electroplating is completed, the solid and liquid are separated, the solid is first washed with deionized water, and then washed with absolute ethanol, and the obtained particles are treated with carbon monoxide for 0.5h, and the pressure of carbon monoxide is ≥0.1MPa. The temperature is 60° C., adding acetone to soak, and separating the solid and liquid to obtain the negative electrode material of the dealloyed sodium ion battery.
实施例2Example 2
本实施例制备了一种去合金化钠离子电池负极材料，其结构由纳米级金属网及其内部支撑的三维多孔碳骨架组成，粒径为1-5μm，其制备过程为：In this example, a de-alloyed sodium-ion battery negative electrode material is prepared. Its structure is composed of a nanoscale metal mesh and a three-dimensional porous carbon skeleton supported inside, with a particle size of 1-5 μm. The preparation process is as follows:
(1)镀前处理：选用粒度≤5μm的聚苯乙烯，加入到15％的氢氧化钠溶液中，煮沸15min(去除表面污物)，去离子水洗涤至中性，再加入到15％的硝酸溶液中，煮沸15min(侵蚀颗粒表面，增强其与镀层的结合能力)，去离子水洗涤至中性，处理过程的固液比为20g/L；(1) Pre-plating treatment: select polystyrene with a particle size of ≤5 μm, add it to 15% sodium hydroxide solution, boil for 15 minutes (to remove surface dirt), wash with deionized water until neutral, and then add 15% sodium hydroxide solution. Boil in nitric acid solution for 15 minutes (to erode the particle surface and enhance its binding ability with the coating), wash with deionized water until neutral, and the solid-to-liquid ratio during the treatment process is 20g/L;
(2)将步骤(1)处理后的聚苯乙烯加入到2.0mol/L的HCl和15g/L的氯 化亚锡溶液中煮沸20min(吸附一层易氧化的亚锡离子)，去离子水洗涤至中性，再加入到1.5mol/L的HCl和1g/L的氯化钯溶液中煮沸20min(钯离子还原为具有活性的金属钯附在颗粒表面)，去离子水洗涤至中性，再加入到30g/L的次磷酸钠溶液中浸泡10min(去除颗粒表面的锡与钯离子)，固液分离后干燥，处理过程的固液比均为40g/L；(2) Add the polystyrene treated in step (1) to 2.0mol/L HCl and 15g/L stannous chloride solution and boil for 20min (adsorbing a layer of easily oxidizable stannous ions), deionized water Wash until neutral, then add to 1.5mol/L HCl and 1g/L palladium chloride solution and boil for 20min (palladium ions are reduced to active metal palladium attached to the particle surface), washed with deionized water until neutral, Then add to 30g/L sodium hypophosphite solution and soak for 10min (to remove tin and palladium ions on the particle surface), dry after solid-liquid separation, and the solid-liquid ratio of the treatment process is 40g/L;
(3)制备含镍合金电镀液：合金电镀液的成分为45g/L的SnCl
2、285g/L的NiCl
2、55g/L的(NH
4)HF
2，pH为2-2.5，电流密度1-2A/dm
2，温度为70℃；
(3) Preparation of nickel-containing alloy electroplating solution: the composition of alloy electroplating solution is 45g/L of SnCl 2 , 285g/L of NiCl 2 , 55g/L of (NH 4 )HF 2 , pH is 2-2.5, current density 1 -2A/dm 2 , the temperature is 70°C;
(4)电镀：将步骤(2)处理好的聚苯乙烯加入到合金电镀液中，在搅拌下施镀，电镀7min；(4) Electroplating: Add the polystyrene processed in step (2) into the alloy electroplating solution, apply plating under stirring, and electroplate for 7 minutes;
(5)去合金化处理：电镀完成后，固液分离，先用去离子水洗涤固体，再采用无水乙醇洗涤，向得到的颗粒通入一氧化碳处理1.0h，一氧化碳的压力≥0.1MPa，处理温度为70℃，加入乙醇浸泡，固液分离后得到去合金化钠颗粒；(5) Dealloying treatment: After the electroplating is completed, the solid and liquid are separated, the solid is first washed with deionized water, and then washed with absolute ethanol, and the obtained particles are treated with carbon monoxide for 1.0h, and the pressure of carbon monoxide is ≥0.1MPa. The temperature is 70°C, add ethanol to soak, and obtain dealloyed sodium particles after solid-liquid separation;
(6)碳化处理：将步骤(5)得到的去合金化钠颗粒进行碳化，碳化为在惰性气氛215℃下反应12h，即得去合金化钠离子电池负极材料。(6) Carbonization treatment: carbonize the dealloyed sodium particles obtained in step (5), and react in an inert atmosphere at 215° C. for 12 hours to obtain a dealloyed sodium ion battery negative electrode material.
实施例3Example 3
本实施例制备了一种去合金化钠离子电池负极材料，其结构由纳米级金属网及其内部支撑的空心碳骨架组成，粒径为1-5μm，其制备过程为：In this example, a de-alloyed sodium-ion battery negative electrode material is prepared. Its structure is composed of a nanoscale metal mesh and a hollow carbon skeleton supported inside it, with a particle size of 1-5 μm. The preparation process is as follows:
(1)镀前处理：选用粒度≤5μm的聚苯乙烯，加入到30％的氢氧化钠溶液中，煮沸30min(去除表面污物)，去离子水洗涤至中性，再加入到25％的硝酸溶液中，煮沸25min(侵蚀颗粒表面，增强其与镀层的结合能力)，去离子水洗涤至中性，处理过程的固液比为30g/L；(1) Pre-plating treatment: select polystyrene with particle size ≤ 5 μm, add to 30% sodium hydroxide solution, boil for 30 minutes (to remove surface dirt), wash with deionized water until neutral, and then add to 25% sodium hydroxide solution In nitric acid solution, boil for 25min (to erode the surface of the particles and enhance their binding ability with the coating), wash with deionized water until neutral, and the solid-liquid ratio during the treatment process is 30g/L;
(2)将步骤(1)处理后的聚苯乙烯加入到2.0mol/L的HCl和20g/L的氯化亚锡溶液中煮沸20min(吸附一层易氧化的亚锡离子)，去离子水洗涤至中性，再加入到2.0mol/L的HCl和1g/L的氯化钯溶液中煮沸20min(钯离子还原为具有活性的金属钯附在颗粒表面)，去离子水洗涤至中性，再加入到50g/L的次磷酸钠溶液中浸泡20min(去除颗粒表面的锡与钯离子)，固液分离后干燥，处理 过程的固液比均为60g/L；(2) Add the polystyrene treated in step (1) to 2.0mol/L HCl and 20g/L stannous chloride solution and boil for 20min (adsorbing a layer of easily oxidizable stannous ions), deionized water Wash until neutral, then add to 2.0mol/L HCl and 1g/L palladium chloride solution and boil for 20min (palladium ions are reduced to active metal palladium attached to the particle surface), washed with deionized water until neutral, Then add it to the sodium hypophosphite solution of 50g/L and soak for 20min (to remove tin and palladium ions on the particle surface), dry after solid-liquid separation, and the solid-liquid ratio in the treatment process is 60g/L;
(3)制备含镍合金电镀液：合金电镀液的成分为30g/L的PbCl
2、45g/L的NiCl
2、50g/L的NH
2SO
3H、120g/L的HEDP、10g/L的盐酸肼、pH为9-10，电流密度0.5-1A/dm
2，温度为25℃；
(3) Preparation of nickel-containing alloy electroplating solution: the composition of the alloy electroplating solution is 30g/L of PbCl 2 , 45g/L of NiCl 2 , 50g/L of NH 2 SO 3 H, 120g/L of HEDP, 10g/L of Hydrazine hydrochloride, pH 9-10, current density 0.5-1A/dm 2 , temperature 25°C;
(4)电镀：将S2处理好的含碳颗粒加入到电镀液中，在搅拌下施镀，电镀8min；(4) Electroplating: Add the carbon-containing particles treated by S2 into the electroplating solution, perform plating under stirring, and electroplate for 8 minutes;
(5)去合金化处理：电镀完成后，固液分离，先用去离子水洗涤固体，再采用无水乙醇洗涤，向得到的颗粒通入一氧化碳处理0.7h，一氧化碳的压力≥0.1MPa，处理温度为80℃，加入***浸泡，固液分离后得到去合金化颗粒；(5) Dealloying treatment: After the electroplating is completed, the solid and liquid are separated, the solid is first washed with deionized water, and then washed with absolute ethanol, and the obtained particles are treated with carbon monoxide for 0.7h, and the pressure of carbon monoxide is ≥0.1MPa. The temperature is 80°C, add ether to soak, and obtain dealloyed particles after solid-liquid separation;
(6)碳化处理：将去合金化颗粒置于二氯甲烷中浸泡，去除内部的聚苯乙烯后，加入到1g/mL的淀粉溶液中，进行水热反应，水热反应的固液比为1g：2mL，反应温度为160℃，反应时间为3h，反应完成后，收集固体后进行碳化，碳化为在惰性气氛215℃下反应12h，即得去合金化钠离子电池负极材料。(6) Carbonization treatment: soak the dealloyed particles in dichloromethane, remove the internal polystyrene, add them to 1g/mL starch solution, and carry out hydrothermal reaction. The solid-to-liquid ratio of the hydrothermal reaction is 1g: 2mL, the reaction temperature is 160°C, and the reaction time is 3h. After the reaction is completed, the solid is collected and then carbonized. The carbonization is carried out in an inert atmosphere at 215°C for 12h, and the dealloyed sodium ion battery negative electrode material is obtained.
对比例comparative example
本对比例用碳热还原法制备了一种Sn/C复合材料，具体过程为：This comparative example prepares a kind of Sn/C composite material by carbothermal reduction method, and concrete process is:
将物质的量比为1:3的SnO
2和活性炭粉置于玛瑙研钵内研磨，混合均匀，混合物装入瓷舟，置于管式炉内，在氩气保护下，以5℃/min升温到950℃，保温8h，然后自然冷却至室温得到Sn/C复合材料。材料主要由Sn圆球颗粒和块片状活性炭组成，Sn圆球均匀分散、吸附在块状活性炭上，Sn圆球颗粒的大小约在0.5-7μm之间。
Grind SnO2 and activated carbon powder with a material ratio of 1:3 in an agate mortar, mix well, put the mixture into a porcelain boat, place it in a tube furnace, and heat it at 5°C/min under the protection of argon. Raise the temperature to 950°C, keep it warm for 8h, and then naturally cool to room temperature to obtain the Sn/C composite material. The material is mainly composed of Sn spherical particles and block-shaped activated carbon. The Sn balls are uniformly dispersed and adsorbed on the block-shaped activated carbon. The size of the Sn spherical particles is about 0.5-7 μm.
试验例Test case
取实施例1-3制得的钠离子电池负极材料和对比例分别制备锂离子电池负极极片，并组装成扣式电池在电流密度为200mA/g、电压范围0.001-2.0V下进行测试，结果如表1所示。Get the sodium-ion battery negative electrode material that embodiment 1-3 makes and comparative example to prepare lithium-ion battery negative electrode sheet respectively, and assemble button battery and test under the current density of 200mA/g, the voltage range 0.001-2.0V, The results are shown in Table 1.
表1Table 1
上面结合附图对本申请实施例作了详细说明，但是本申请不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本申请宗旨的前提下作出各种变化。此外，在不冲突的情况下，本申请的实施例及实施例中的特征可以相互组合。The embodiments of the present application have been described in detail above in conjunction with the accompanying drawings, but the present application is not limited to the above-mentioned embodiments, and within the scope of knowledge of those of ordinary skill in the art, various modifications can be made without departing from the purpose of the present application. Variety. In addition, the embodiments of the present application and the features in the embodiments can be combined with each other under the condition of no conflict.
Claims (10)
- 一种去合金化钠离子电池负极材料，其中，由实心碳粒及包覆于所述实心碳粒表面的纳米级金属网组成，或由纳米级金属网及其内部支撑的碳骨架组成，所述碳骨架为空心状或三维多孔状，所述纳米级金属网的组成为Sn、Pb、Bi、Ge或Sb中的至少一种。A de-alloyed sodium-ion battery negative electrode material, wherein, it is composed of solid carbon particles and nano-scale metal mesh coated on the surface of the solid carbon particles, or composed of nano-scale metal mesh and its internally supported carbon skeleton, the The carbon skeleton is hollow or three-dimensional porous, and the composition of the nanoscale metal mesh is at least one of Sn, Pb, Bi, Ge or Sb.
- 根据权利要求1所述的去合金化钠离子电池负极材料，其中，所述去合金化钠离子电池负极材料的粒径为1-5μm。The negative electrode material for dealloyed sodium ion battery according to claim 1, wherein the particle size of the negative electrode material for dealloyed sodium ion battery is 1-5 μm.
- 如权利要求1所述的去合金化钠离子电池负极材料的制备方法，其中，包括以下步骤：The preparation method of dealloyed sodium ion battery negative electrode material as claimed in claim 1, wherein, comprises the following steps:S1：将含碳颗粒加入到盐酸与氯化亚锡的混合溶液中煮沸一段时间，洗涤后加入到盐酸与氯化钯的混合溶液中煮沸一段时间，洗涤后再加入到次磷酸钠溶液中浸泡，固液分离，得到表面附有金属钯层的含碳颗粒；所述含碳颗粒为硬碳或有机聚合物；S1: Add the carbon-containing particles to the mixed solution of hydrochloric acid and stannous chloride and boil for a period of time. After washing, add them to the mixed solution of hydrochloric acid and palladium chloride and boil for a period of time. After washing, add them to the solution of sodium hypophosphite for soaking , solid-liquid separation to obtain carbon-containing particles with a metal palladium layer on the surface; the carbon-containing particles are hard carbon or organic polymers;S2：将所述表面附有金属钯层的含碳颗粒加入到电镀液中，在搅拌下施镀，得到具有合金镀层的含碳颗粒；所述电镀液中含有Ni以及Sn、Pb、Bi、Ge或Sb中的至少一种；S2: Add the carbon-containing particles with a metal palladium layer on the surface to the electroplating solution, and perform plating under stirring to obtain carbon-containing particles with an alloy coating; the electroplating solution contains Ni and Sn, Pb, Bi, At least one of Ge or Sb;S3：向所述具有合金镀层的含碳颗粒通入一氧化碳处理，再加入到第一有机溶剂中浸泡，得到去合金化颗粒；当所述含碳颗粒为有机聚合物时，进行步骤S4；S3: injecting carbon monoxide into the carbon-containing particles with an alloy coating, and then soaking in the first organic solvent to obtain de-alloyed particles; when the carbon-containing particles are organic polymers, proceed to step S4;S4：选择以下任一种方法进行：(1)将所述去合金化颗粒在惰性气氛下进行碳化，即得；(2)将所述去合金化颗粒置于第二有机溶剂中浸泡，直至除去内部的含碳颗粒后，再置于碳源溶液中进行水热反应，然后在惰性气氛下进行碳化，即得；其中，方法(2)中使用的含碳颗粒为可溶性线型有机聚合物。S4: Choose any of the following methods: (1) carbonize the dealloyed particles in an inert atmosphere; (2) soak the dealloyed particles in a second organic solvent until After removing the internal carbon-containing particles, place them in a carbon source solution for hydrothermal reaction, and then carry out carbonization under an inert atmosphere to obtain that; wherein, the carbon-containing particles used in method (2) are soluble linear organic polymers .
- 根据权利要求3所述的制备方法，其中，步骤S1中，所述含碳颗粒经过以下前处理：将所述含碳颗粒加入到氢氧化钠溶液中加热，用水洗涤后，再加入到硝酸溶液中加热，再用水洗涤。The preparation method according to claim 3, wherein, in step S1, the carbon-containing particles undergo the following pretreatment: adding the carbon-containing particles to a sodium hydroxide solution for heating, washing with water, and then adding to a nitric acid solution Heat in medium and wash with water.
- 根据权利要求3所述的制备方法，其中，步骤S1中，所述含碳颗粒的粒度≤5μm。The preparation method according to claim 3, wherein, in step S1, the particle size of the carbon-containing particles is ≤5 μm.
- 根据权利要求3所述的制备方法，其中，步骤S1中，所述盐酸与氯化亚锡的混合溶液中盐酸的浓度为1.5-2.0mol/L，氯化亚锡的浓度为15-20g/L。The preparation method according to claim 3, wherein, in step S1, the concentration of hydrochloric acid in the mixed solution of the hydrochloric acid and stannous chloride is 1.5-2.0mol/L, and the concentration of stannous chloride is 15-20g/L L.
- 根据权利要求3所述的制备方法，其中，步骤S1中，所述盐酸与氯化钯的混合溶液中盐酸的浓度为1.5-2.0mol/L，氯化钯的浓度为0.5-1g/L。The preparation method according to claim 3, wherein, in step S1, the concentration of hydrochloric acid in the mixed solution of hydrochloric acid and palladium chloride is 1.5-2.0mol/L, and the concentration of palladium chloride is 0.5-1g/L.
- 根据权利要求3所述的制备方法，其中，步骤S1中，所述有机聚合物为聚苯乙烯、聚乙炔、聚苯胺、聚吡咯或聚噻吩中的至少一种。The preparation method according to claim 3, wherein, in step S1, the organic polymer is at least one of polystyrene, polyacetylene, polyaniline, polypyrrole or polythiophene.
- 根据权利要求3所述的制备方法，其特征在于，步骤S3中，所述第一有机溶剂为苯、丙酮、***、四氯化萘、乙醇、三氯甲烷或四氯化碳中的至少一种。The preparation method according to claim 3, wherein, in step S3, the first organic solvent is at least one of benzene, acetone, ether, tetrachlorinated naphthalene, ethanol, chloroform or carbon tetrachloride kind.
- 根据权利要求3所述的制备方法，其中，步骤S4中，所述碳源溶液为葡萄糖、淀粉、蔗糖、果糖、乳糖或半乳糖的溶液中的至少一种。The preparation method according to claim 3, wherein, in step S4, the carbon source solution is at least one of solutions of glucose, starch, sucrose, fructose, lactose or galactose.
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| CN108493403A (en) * | 2018-05-17 | 2018-09-04 | 中山大学 | A kind of synthetic method of self-supporting sodium-ion battery cathode |
| CN108695498A (en) * | 2018-05-16 | 2018-10-23 | 东北大学秦皇岛分校 | A kind of porous carbon embeds the cell negative electrode material and preparation method thereof of kamash alloy |
| CN108987688A (en) * | 2018-06-22 | 2018-12-11 | 清华大学深圳研究生院 | A kind of C-base composte material, preparation method and sodium-ion battery |
| CN109817920A (en) * | 2019-01-22 | 2019-05-28 | 陕西科技大学 | A kind of preparation method and application of selenium enveloped carbon nanometer tube/graphene |
| US20190165365A1 (en) * | 2017-11-30 | 2019-05-30 | Nanotek Instruments, Inc. | Anode Particulates or Cathode Particulates and Alkali Metal Batteries Containing Same |
| CN114725387A (en) * | 2022-02-21 | 2022-07-08 | 广东邦普循环科技有限公司 | Dealloying sodium ion battery cathode material and preparation method thereof |
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| US20190165365A1 (en) * | 2017-11-30 | 2019-05-30 | Nanotek Instruments, Inc. | Anode Particulates or Cathode Particulates and Alkali Metal Batteries Containing Same |
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| CN108493403A (en) * | 2018-05-17 | 2018-09-04 | 中山大学 | A kind of synthetic method of self-supporting sodium-ion battery cathode |
| CN108987688A (en) * | 2018-06-22 | 2018-12-11 | 清华大学深圳研究生院 | A kind of C-base composte material, preparation method and sodium-ion battery |
| CN109817920A (en) * | 2019-01-22 | 2019-05-28 | 陕西科技大学 | A kind of preparation method and application of selenium enveloped carbon nanometer tube/graphene |
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