CN114649150A - Three-dimensional silicon substrate/transition metal compound based composite electrode material, preparation method and application - Google Patents
Three-dimensional silicon substrate/transition metal compound based composite electrode material, preparation method and application Download PDFInfo
- Publication number
- CN114649150A CN114649150A CN202210232093.5A CN202210232093A CN114649150A CN 114649150 A CN114649150 A CN 114649150A CN 202210232093 A CN202210232093 A CN 202210232093A CN 114649150 A CN114649150 A CN 114649150A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- metal compound
- dimensional silicon
- electrode material
- composite electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 204
- 239000010703 silicon Substances 0.000 title claims abstract description 204
- 239000007772 electrode material Substances 0.000 title claims abstract description 77
- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 64
- 239000000758 substrate Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 38
- -1 transition metal sulfide Chemical class 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002848 electrochemical method Methods 0.000 claims abstract description 14
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000004070 electrodeposition Methods 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 239000003792 electrolyte Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 150000003624 transition metals Chemical class 0.000 claims description 14
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 13
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 13
- 229910052711 selenium Inorganic materials 0.000 claims description 12
- 239000011669 selenium Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000004146 energy storage Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical group O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 150000003346 selenoethers Chemical class 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000007769 metal material Substances 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
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 130
- 239000000243 solution Substances 0.000 description 67
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 52
- 239000008367 deionised water Substances 0.000 description 38
- 229910021641 deionized water Inorganic materials 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 36
- 238000005530 etching Methods 0.000 description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 238000002791 soaking Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 238000009713 electroplating Methods 0.000 description 14
- 239000002070 nanowire Substances 0.000 description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 10
- 229910001961 silver nitrate Inorganic materials 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 6
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 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 description 4
- 239000013543 active substance Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PYHYDDIOBZRCJU-UHFFFAOYSA-N [Ni]=[Se].[Co] Chemical compound [Ni]=[Se].[Co] PYHYDDIOBZRCJU-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- LOUWOZBMDAQCRT-UHFFFAOYSA-N cobalt sulfanylideneiron Chemical compound [S].[Fe].[Co] LOUWOZBMDAQCRT-UHFFFAOYSA-N 0.000 description 1
- HSQIWKNMXNBSTL-UHFFFAOYSA-J cobalt(2+);iron(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Co+2] HSQIWKNMXNBSTL-UHFFFAOYSA-J 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- QJSRJXPVIMXHBW-UHFFFAOYSA-J iron(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Ni+2] QJSRJXPVIMXHBW-UHFFFAOYSA-J 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a three-dimensional silicon matrix/transition metal compound-based composite electrode, a preparation method and application thereof, wherein the transition metal compound comprises transition metal sulfide, transition metal selenide or a mixture of the transition metal sulfide and the transition metal selenide. The main preparation method is to directly or indirectly prepare the transition metal compound on a three-dimensional silicon substrate by an electrochemical method, a hydrothermal method or a high-temperature calcination method. According to different designs and preparation of electrode structures, the three-dimensional silicon substrate/transition metal compound electrode material prepared by the invention can be respectively applied to energy conversion and storage devices.
Description
Technical Field
The invention belongs to the field of electrode materials, and relates to a method for preparing a transition metal compound on a three-dimensional silicon substrate by a hydrothermal method, an electrochemical method or a high-temperature calcination method.
Background
With the development of the times, the appearance of innovative miniature portable devices in recent years, such as the wide application of technologies such as wireless microsensors or biomedical implanted micro devices, has attracted great interest in the field of energy storage devices. Electrochemical systems, including electrochemical supercapacitors, are particularly popular because they are more sustainable and environmentally friendly. Supercapacitors are a good choice for integration with other energy storage materials for energy conversion and storage systems because they exhibit excellent performance due to their high power density, low weight, rapid response to potential changes, high cycle life and long term stability, which can easily exceed one million operating cycles. Silicon is an ideal electrode material of a micro super capacitor for chip energy storage, and the three-dimensional silicon substrate has the advantages of small size and large specific surface area, and is beneficial to carrying more electrode active substances. Due to its ultra-high theoretical capacity, high working potential and abundant resources, silicon has been developed as the most ideal anode candidate for lithium ion batteries. However, the silicon material has large volume expansion and poor conductivity, which hinders practical application thereof.
In recent years, transition metal compounds have been popular in preparing electrode materials of super capacitors due to their unique physical and chemical properties, such as transition metal sulfides and selenides, which have high electrical conductivity and specific capacitance. To date, transition metal sulfides and transition metal selenides among transition metal compounds are widely used for preparing electrode materials of supercapacitors, such as cobalt sulfide, nickel sulfide, copper sulfide, nickel cobalt selenide, nickel selenide and the like. Binary transition metal compounds have more oxidation states and therefore more oxidation active sites than monometallic compounds. Transition metal sulfides and transition metal selenides have lower optical bandgaps and therefore higher conductivities and flexibility than transition metal oxides.
The transition metal compound is combined with the three-dimensional silicon matrix, so that good electrochemical performance can be obtained, and the transition metal compound is favorably used as an energy storage electrode material or an energy conversion electrode material. Moreover, many electronic components are currently manufactured using silicon as a raw material,
the transition metal compound electrode material prepared by taking silicon as a substrate is beneficial to being integrated with other electronic elements, and the preparation of a miniaturized integrated device is beneficial to making a contribution to the current demand of the miniaturized device.
Disclosure of Invention
One of the purposes of the invention is to provide a three-dimensional silicon substrate/transition metal compound based composite electrode material and a preparation method thereof, so that an active substance is directly contacted with a silicon substrate, and the internal resistance is effectively reduced. The composite material is also used in the fields of energy storage electrode materials or energy conversion electrode materials and the like.
The three-dimensional silicon substrate/transition metal compound based composite electrode material is characterized in that a transition metal compound is prepared on the surface of a three-dimensional silicon substrate, the transition metal is one or more of transition metal materials such as nickel, cobalt, manganese, iron and the like, and the transition metal compound is a sulfide, a selenide or a mixture of the sulfide and the selenide of the transition metal compound.
And further, the charge collection layer is positioned between the three-dimensional silicon matrix and the transition metal compound layer to form a composite electrode material in a structure of 'three-dimensional silicon matrix/charge collection layer/transition metal compound', or positioned on the transition metal compound to form a composite electrode material in a structure of 'three-dimensional silicon matrix/transition metal compound/charge collection layer'.
Further, the conductive material is a conductive polymer, a carbon layer or a metal layer; the conductive polymer is prepared by an electrochemical method or a spin-coating method and is polypyrrole, polythiophene or polyaniline; the carbon layer is prepared by a spin coating method, a high-temperature calcination method or a hydrothermal method and is graphene, a conductive carbon layer or a carbon nano tube; the metal layer is prepared by a CVD method, an ALD method or an electrochemical method and is metallic nickel or TiN.
The preparation method of the three-dimensional silicon substrate/transition metal compound based composite electrode material is characterized in that the transition metal compound is prepared by an electrochemical method, the three-dimensional silicon substrate or the three-dimensional silicon substrate modified with a charge collection layer is taken as a working electrode, Pt is taken as a counter electrode, Ag/AgCl is taken as a reference electrode, and electrochemical deposition is carried out under the voltage of-1V; the electrolyte used for electrochemical deposition comprises transition metal salt and a sulfur source and/or a selenium source, or two electrolytes containing the transition metal salt and the sulfur source, the transition metal salt and the selenium source are alternately electrochemically deposited, and the electrodeposition time is 5-1200 s.
The preparation method based on the three-dimensional silicon matrix/transition metal compound composite electrode material is characterized in that the total concentration of transition metal salt in electrolyte is 0.02-0.2 mol/L, the content of sulfur source is 1-6 times of that of the transition metal salt, and the content of selenium source is 5-50% of that of the transition metal salt.
The preparation method of the three-dimensional silicon substrate/transition metal compound-based composite electrode material is characterized in that the transition metal compound is prepared by a hydrothermal method, namely the three-dimensional silicon structure/transition metal hydroxide precursor is put into a solution containing a sulfur source or a selenium source for hydrothermal reaction.
The preparation method of the three-dimensional silicon substrate/transition metal compound based composite electrode material is characterized in that the transition metal compound is prepared by adopting a high-temperature calcination method, namely, the three-dimensional silicon structure/transition metal hydroxide precursor is placed into a high-temperature tube furnace, a sulfur source or a selenium source is placed at the upstream, and high-temperature calcination is carried out in the atmosphere of nitrogen to prepare the three-dimensional silicon structure/transition metal compound electrode material; wherein the heating rate of the high-temperature calcination is 2-8 ℃/min, the heat preservation temperature is 300-450 ℃, and the heat preservation time is 0.5-2.5 h.
Further, the three-dimensional silicon structure/transition metal hydroxide precursor is prepared by a hydrothermal method or an electrochemical method, the electrochemical method being: firstly, taking a three-dimensional silicon substrate or the three-dimensional silicon substrate modified with a charge collection layer as a working electrode, Pt as a counter electrode and Ag/AgCl as a reference electrode, and carrying out electrochemical deposition for 10-500 s in an electrolyte containing transition metal salt and hexadecyl trimethyl ammonium bromide under the voltage of-1V to prepare a three-dimensional silicon substrate/transition metal hydroxide precursor; wherein the total concentration of the transition metal salt in the electrolyte is 0.08-0.15 mol/L.
Further, the sulfur source is one of thioacetamide, thiourea and sublimed sulfur; the selenium source is selenium dioxide and/or selenium powder.
The application of the three-dimensional silicon matrix/transition metal compound-based composite electrode material is characterized in that the composite electrode material with the structure of the three-dimensional silicon matrix/transition metal compound/charge collection layer is used as an energy storage electrode material and/or an energy conversion electrode material, and the prepared composite electrode material with the structure of the three-dimensional silicon matrix/charge collection layer/transition metal compound is used as an energy storage electrode material.
The invention has the beneficial effects that:
(1) the invention adopts electrochemical deposition method or hydrothermal deposition method to directly prepare transition metal compound on the three-dimensional silicon substrate, and the method for self-growing active substance avoids the use of binder, so that the active substance is directly contacted with the silicon substrate, and the internal resistance is effectively reduced.
(2) The invention modifies metal layer, carbon layer or high conducting layer on the three-dimensional silicon substrate, which can protect the silicon substrate from oxidation and corrosion; and secondly, the silicon substrate is equivalent to a bracket, and any silicon wafer can be used as the substrate, so that the cost of raw materials is reduced.
(3) The transition metal compound is prepared by different methods, and compared with the transition metal hydroxide, the transition metal compound has higher conductivity and specific capacitance, and the cyclic stability of the transition metal compound is better than that of the transition metal hydroxide. Meanwhile, the transition metal compound is prepared on the three-dimensional silicon structure, so that the stacking of the transition metal compound can be effectively prevented, the contact specific surface area is increased, the contact with an electrolyte in a redox reaction is facilitated, and the internal resistance is effectively reduced. Compared with single transition metal compounds, the multi-transition metal compounds can play a synergistic role, and the specific electrochemical performance of the electrode material is favorably improved.
(4) The three-dimensional silicon structure/transition metal compound prepared by the invention has higher electrochemical performance and is beneficial to being used as an energy storage electrode material and an energy conversion electrode material.
Drawings
FIG. 1: example 2 preparation by electrochemical deposition method based on metallic nickel modified three-dimensional silicon structure/nickel cobalt selenide electrode material (a) CV curve of 10 mV/s; (b) GCD curve at 1A/g current density; (c) impedance graph.
Fig. 2 is an SEM image of 10000 times enlargement of the metallic nickel modified three-dimensional silicon structure/nickel cobalt sulfide electrode material prepared by the electrochemical deposition method in example 3 under a field emission scanning electron microscope.
FIG. 3: example 3 a CV curve of 10mV/s based on a metallic nickel modified three-dimensional silicon structure/nickel cobalt sulfide electrode material prepared by an electrochemical deposition process; (b) GCD curve at 1A/g current density; (c) impedance graph.
FIG. 4: example 5 a CV curve of (a)10mV/s based on metallic nickel modified three-dimensional silicon structure/nickel cobalt sulfide electrode material prepared by hydrothermal method; (b) GCD curve at 1A/g current density; (c) impedance graph.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and preferred embodiments. It should be understood that the preferred embodiments described herein are illustrative only and are not limiting.
Example 1
(1) And etching by a solution method to manufacture a three-dimensional silicon wafer, and carrying out secondary treatment on the three-dimensional silicon wafer.
(a) Selecting a metallurgical-grade silicon wafer, cutting the metallurgical-grade silicon wafer into sample wafers with the size of 2cm multiplied by 2.5cm, washing the sample wafers with isopropanol, and then adding concentrated sulfuric acid and hydrogen peroxide into the sample wafers with the weight ratio of 3: 1 soaking in the solution for 20min, washing with deionized water, and spin-drying at high speed; and etching the substrate for 60min in an etching solution containing 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon wafer into a TMAH solution for secondary treatment to obtain the three-dimensional silicon wafer, wherein the treatment time is 1h, and the treatment temperature is 20 ℃. Wherein the volume ratio of TMAH, isopropanol and deionized water in the TMAH solution is 0.3:5: 25.
(2) And (3) electrochemically preparing the three-dimensional silicon matrix/transition metal sulfide composite electrode material.
(a) Electroplating of metallic nickel layers
0.2mol/L of NiSO4·6H2O, 0.05mol/L NH4And taking a mixed solution prepared by Cl and 0.025mol/L Sodium Dodecyl Sulfate (SDS) as an electrolyte, taking a silicon wafer as a working electrode and Pt as a counter electrode under the bias voltage of 3V, and stretching the three-dimensional silicon wafer into the electrolyte according to the specification of 2cm multiplied by 2cm, wherein the electroplating time is 8 min.
(b) Preparation of transition metal sulfide by electrodeposition
0.08mol/L nickel nitrate hexahydrate, 0.04mol/L cobalt nitrate hexahydrate and 0.75mol/L thiourea were added to 30ml of deionized water. In a three-electrode system, a three-dimensional silicon wafer is used as a working electrode, Pt is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode for electrochemical deposition, the area of the three-dimensional silicon wafer entering electrolyte is 1cm multiplied by 1cm, and the electrodeposition time is 300 s.
Example 2
(1) And etching by a solution method to manufacture a three-dimensional silicon wafer, and carrying out secondary treatment on the three-dimensional silicon wafer.
(a) Selecting a metallurgical grade silicon wafer, cutting into sample wafers with the size of 2cm multiplied by 2.5cm, washing with isopropanol, and then adding a solvent of concentrated sulfuric acid and hydrogen peroxide in a proportion of 3: 1 soaking in the solution for 20min, washing with deionized water, and spin-drying at high speed; and etching the substrate for 60min in an etching solution containing 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon wafer into a TMAH solution for secondary treatment, wherein the treatment time is 1h, and the treatment temperature is 20 ℃. Wherein the volume ratio of TMAH, isopropanol and deionized water in the TMAH solution is 0.3:5: 25.
(2) And (3) electrochemically preparing the three-dimensional silicon structure/transition metal selenide composite electrode material.
(a) Electroplating metallic nickel layer with 0.2mol/L NiSO4·6H2O, 0.05mol/L NH4A solution prepared by mixing Cl and 0.025mol/L Sodium Dodecyl Sulfate (SDS) was used as an electrolyte. Under the bias voltage of 3V, a silicon wafer is taken as a working electrode, Pt is taken as a counter electrode, the silicon wafer is stretched into the electrolyte according to the specification of 2cm multiplied by 2cm, and the electroplating time is 8 min.
(b) Preparation of transition metal selenides by electrodeposition
0.08mol/L nickel nitrate hexahydrate, 0.04mol/L cobalt nitrate hexahydrate and 0.04mol/L selenium dioxide were added to 30ml of deionized water. In a three-electrode system, a three-dimensional silicon wafer is used as a working electrode, Pt is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode for electrochemical deposition, the area of the three-dimensional silicon wafer entering electrolyte is 1cm multiplied by 1cm, and the electrodeposition time is 300 s.
Fig. 2 shows the electrochemical performance of the three-dimensional silicon structure/nickel cobalt selenide composite electrode material prepared by example 2. Wherein, the CV curve of the graph (a) has obvious oxidation-reduction peak, and the specific capacitance is 820F/g under the scanning rate of 10 mV/s; (b) the GCD curve of the graph is a symmetrical triangle-like shape, showing the capacitive behavior of the electrode material, which has a specific capacitance of 1084.22F/g at a current density of 1A/g; (c) the internal resistance of the electrode material is 2.29 omega.
Example 3
(1) Etching by solution method to make three-dimensional silicon wafer, and secondary treatment
(a) Selecting a metallurgical-grade silicon wafer, cutting the silicon wafer into sample wafers of 2cm multiplied by 2.5cm, washing the sample wafers with isopropanol, and then carrying out reaction on concentrated sulfuric acid and hydrogen peroxide in a concentration ratio of 3: 1 soaking in the solution for 20min, washing with deionized water, and spin-drying at high speed; and etching the substrate for 60min in an etching solution containing 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon wafer into a TMAH solution for secondary treatment to obtain a three-dimensional silicon wafer, wherein the treatment time is 1h, and the treatment temperature is 20 ℃. Wherein the volume ratio of TMAH, isopropanol and deionized water in the TMAH solution is 0.3:5: 25.
(2) The composite electrode material with a three-dimensional silicon substrate/charge collection layer/transition metal sulfide structure is characterized in that the charge collection layer is a metal nickel layer.
(a) Electroplating metallic nickel layer with 0.2mol/L NiSO4·6H2O, 0.05mol/L NH4A solution prepared by mixing Cl and 0.025mol/L Sodium Dodecyl Sulfate (SDS) was used as an electrolyte. Under the bias voltage of 3V, a silicon wafer is taken as a working electrode, Pt is taken as a counter electrode, the three-dimensional silicon wafer is stretched into electrolyte according to the specification of 2cm multiplied by 2cm, and the electroplating time is 8 min.
(b) Preparation of transition metal sulfide by electrodeposition
0.08mol/L nickel nitrate hexahydrate, 0.04mol/L cobalt nitrate hexahydrate and 0.75mol/L thiourea were added to 30ml of deionized water. In a three-electrode system, a silicon wafer is used as a working electrode, Pt is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode for electrochemical deposition, the area of the silicon wafer entering electrolyte is 1cm multiplied by 1cm, and the electrodeposition time is 300 s.
Fig. 2 is an SEM image of nickel cobalt sulfide in the metal nickel modified three-dimensional silicon structure/nickel cobalt sulfide electrode material, which is magnified 20000 times, and we can clearly see that the nickel cobalt sulfide of the lamella is tightly wrapped on the surface of the silicon nanowire, although the top of the silicon nanowire is slightly stacked, the whole specific surface area is larger, which is beneficial to exposing more active sites, and fully generating redox reaction, so that the specific capacitance is increased.
Fig. 3 shows the electrochemical performance of the metallic nickel-modified three-dimensional silicon structure/nickel cobalt sulfide electrode material prepared by example 3. Wherein, the CV curve of the graph (a) has two groups of obvious oxidation-reduction peaks (Co)2+/Co3+,Ni2+/Ni3+) The specific capacitance was 1191.42F/g at a scan rate of 10 mV/s;(b) the GCD curve of the graph is a symmetrical triangular-like shape, illustrating the pronounced capacitive behavior of the electrode, the electrode material having a specific capacitance of 1780.24F/g at a current density of 1A/g; (c) the internal resistance of the electrode material is 2.75 omega.
Example 4
(1) And etching by a solution method to manufacture a three-dimensional silicon wafer, and carrying out secondary treatment on the three-dimensional silicon wafer.
(a) Selecting a metallurgical-grade silicon wafer, cutting the silicon wafer into sample wafers of 1cm multiplied by 2cm, washing the sample wafers with isopropanol, and then treating the sample wafers with concentrated sulfuric acid and hydrogen peroxide in a concentration of 3: 1 soaking in the solution for 20min, washing with deionized water, and spin-drying at high speed; and etching the substrate for 60min in an etching solution containing 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon wafer into a TMAH solution for secondary treatment for 1h to obtain a three-dimensional silicon wafer, wherein the treatment temperature is 20 ℃. Wherein the volume ratio of TMAH, isopropanol and deionized water in the TMAH solution is 0.3:5: 25.
(2) Preparing the composite electrode material with a three-dimensional silicon substrate/charge collection layer/transition metal selenide structure, wherein the charge collection layer is an activated carbon layer.
(a) High temperature carbon layer preparation
200mg of glucose was dispersed in 15ml of a mixed solution of deionized water and ethanol at a volume ratio of 1:2, and sonication was continued for 30 min. The dispersed glucose solution was then poured into a previously placed three-dimensional silicon wafer (1 x 2 cm)2) The autoclave was maintained at 200 ℃ for 24 hours. Subsequently, the carbon film was annealed by heating at 500 ℃ for 2 hours in a high-temperature tube furnace in a nitrogen atmosphere to form an activated carbon layer.
(b) Preparation of transition metal selenides by electrodeposition
0.1mol/L cobalt nitrate hexahydrate and 0.75mol/L thiourea were added to 30ml deionized water as an electrolyte. In a three-electrode system, a silicon wafer is used as a working electrode, Pt is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode for electrochemical deposition, the area of the silicon wafer entering an electrolyte is 1cm multiplied by 1cm, and the electrodeposition time is 300 s.
Example 5
(1) And etching by a solution method to manufacture a three-dimensional silicon wafer, and carrying out secondary treatment on the three-dimensional silicon wafer.
(a) Selecting a metallurgical-grade silicon wafer, cutting the silicon wafer into sample wafers of 1cm multiplied by 2cm, washing the sample wafers with isopropanol, and then treating the sample wafers with concentrated sulfuric acid and hydrogen peroxide in a concentration of 3: 1 soaking in the solution for 20min, washing with deionized water, and spin-drying at high speed; and etching the substrate for 60min in an etching solution containing 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon wafer into a TMAH solution for secondary treatment for 1h to obtain a three-dimensional silicon wafer, wherein the treatment temperature is 20 ℃. Wherein the volume ratio of TMAH, isopropanol and deionized water in the TMAH solution is 0.3:5: 25.
(2) Electroplating of metallic nickel layers
0.2mol/L of NiSO4·6H2O, 0.05mol/L NH4Cl and 0.025mol/L SDS. Under the bias voltage of 3V, taking a silicon wafer as a working electrode and Pt as a counter electrode, and stretching the silicon wafer into electrolyte according to the specification of 2cm multiplied by 2cm, wherein the electroplating time is 10 min; the electroplated metal nickel layer is used as a charge collection layer.
(3) Preparing the three-dimensional silicon structure/charge collection layer/transition metal sulfide composite electrode material by a hydrothermal and deposition method.
(a) Electro-deposition nickel, cobalt double hydroxide precursor
0.06mol/L nickel nitrate hexahydrate and 0.06mol/L cobalt nitrate hexahydrate are added into 30ml deionized water. In a three-electrode system, a silicon wafer is used as a working electrode, Pt is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode for electrochemical deposition, the area of the three-dimensional silicon wafer entering an electrolyte is 1cm multiplied by 1cm, and the electrodeposition time is 300 s.
(b) Hydrothermal method for preparing nickel and cobalt sulfide
Preparing 20ml of 0.01mol/L sodium sulfide nonahydrate solution, and putting the nickel-cobalt double hydroxide precursor prepared by the electrochemical method into the sodium sulfide nonahydrate solution, and keeping the temperature at 60 ℃ for 30 min.
Fig. 4 shows the electrochemical performance of the three-dimensional silicon structure/nickel cobalt sulfide composite electrode material prepared by hydrothermal method of example 5. Wherein, the specific capacitance of graph (a) is 692.85F/g at a scan rate of 10 mV/s; (b) the GCD curve of the graph is a symmetrical triangular-like shape, illustrating the pronounced capacitive behavior of the electrode, the electrode material having a specific capacitance of 1206.02F/g at a current density of 1A/g; (c) the internal resistance of the electrode material is 2.65 omega.
Example 6
(1) And etching by a solution method to manufacture a three-dimensional silicon wafer, and carrying out secondary treatment on the three-dimensional silicon wafer.
(a) Selecting a metallurgical-grade silicon wafer, cutting the silicon wafer into 1cm by 2cm sample wafers, washing the sample wafers with isopropanol, and then carrying out reaction on concentrated sulfuric acid and hydrogen peroxide in a reaction condition of 3: 1 soaking in the solution for 20min, washing with deionized water, and spin-drying at high speed; and etching the substrate for 60min in an etching solution containing 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon wafer into a TMAH solution for secondary treatment for 1h to obtain a three-dimensional silicon wafer, wherein the treatment temperature is 20 ℃. Wherein the volume ratio of TMAH, isopropanol and deionized water in the TMAH solution is 0.3:5: 25.
(2) Electroplating of metallic nickel layers
0.2mol/L of NiSO4·6H2O, 0.05mol/L NH4Cl and 0.025mol/L SDS. Under the bias voltage of 3V, a silicon wafer is taken as a working electrode, Pt is taken as a counter electrode, the silicon wafer is stretched into the electrolyte according to the specification of 2cm multiplied by 2cm, and the electroplating time is 10 min. The electroplated metallic nickel layer is used as a charge collection layer.
(3) Hydrothermal and deposition method for preparing three-dimensional silicon structure/transition metal sulfide composite electrode material
(a) Electro-deposition nickel, iron double hydroxide precursor
0.08mol/L nickel nitrate hexahydrate and 0.04mol/L ferric nitrate hexahydrate are added into 30ml deionized water. In a three-electrode system, a silicon wafer is used as a working electrode, Pt is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode for electrochemical deposition, the area of the three-dimensional silicon wafer entering an electrolyte is 1cm multiplied by 1cm, and the electrodeposition time is 300 s.
(b) Hydrothermal method for preparing transition metal sulfide
Preparing 20ml of 0.01mol/L sodium sulfide nonahydrate solution, and putting the nickel iron hydroxide precursor prepared by the electrochemical method into the sodium sulfide nonahydrate solution at the temperature of 60 ℃ for 30 min.
Example 7
(1) Etching by solution method to make three-dimensional silicon wafer, and secondary treatment
(a) Selecting a metallurgical-grade silicon wafer, cutting the silicon wafer into 1cm by 2cm sample wafers, washing the sample wafers with isopropanol, and then carrying out reaction on concentrated sulfuric acid and hydrogen peroxide in a reaction condition of 3: 1 soaking in the solution for 20min, washing with deionized water, and spin-drying at high speed; and etching the substrate for 60min in an etching solution containing 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) And (3) immersing the silicon wafer into a TMAH solution for secondary treatment for 1h to obtain a three-dimensional silicon wafer, wherein the treatment temperature is 20 ℃. Wherein the volume ratio of TMAH, isopropanol and deionized water in the TMAH solution is 0.3:5: 25.
(2) High temperature carbon layer preparation
200mg of glucose was dispersed in 15ml of a mixed solution of deionized water and ethanol at a volume ratio of 1:2, and sonication was continued for 30 min. Then the dispersed glucose solution was poured into the previously deposited three-dimensional silica matrix (1 x 2 cm)2) The autoclave was maintained at 200 ℃ for 24 hours. Then, heating and annealing for 2h at 500 ℃ in a high-temperature tube furnace in a nitrogen atmosphere to form an activated carbon layer;
(3) hydrothermal and deposition method for preparing three-dimensional silicon structure/transition metal sulfide composite electrode material
(a) Electro-deposition of cobalt and iron double hydroxide precursor
0.06mol/L ferric nitrate hexahydrate and 0.06mol/L cobalt nitrate hexahydrate were added to 30ml deionized water. In a three-electrode system, a three-dimensional silicon wafer is used as a working electrode, Pt is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode for electrochemical deposition, the area of the three-dimensional silicon wafer entering electrolyte is 1cm multiplied by 1cm, and the electrodeposition time is 300 s.
(b) Hydrothermal method for preparing cobalt iron sulfide
Preparing 20ml of 0.015mol/L sodium sulfide nonahydrate solution, and putting the cobalt-iron hydroxide precursor prepared by the electrochemical method into the sodium sulfide nonahydrate solution, wherein the temperature is 60 ℃, and keeping the solution for 30 min.
Example 8
(1) Etching by solution method to make three-dimensional silicon wafer, and secondary treatment
(a) Selecting a metallurgical-grade silicon wafer, cutting the silicon wafer into 1cm by 2cm sample wafers, washing the sample wafers with isopropanol, and then carrying out reaction on concentrated sulfuric acid and hydrogen peroxide in a reaction condition of 3: 1 soaking in the solution for 20min, washing with deionized water, and spin-drying at high speed; and etching the substrate for 60min in an etching solution containing 5mol/L and 0.02mol/L of silver nitrate at normal temperature and normal pressure.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon wafer into a TMAH solution for secondary treatment for 1h to obtain a three-dimensional silicon wafer, wherein the treatment temperature is 20 ℃. Wherein the volume ratio of TMAH, isopropanol and deionized water in the TMAH solution is 0.3:5: 25.
(2) Electroplating of metallic nickel layers
0.2M of NiSO4·6H2O, 0.05mol/L NH4Cl and 0.025mol/L SDS. Under the bias voltage of 3V, taking a silicon wafer as a working electrode and Pt as a counter electrode, and stretching the silicon wafer into electrolyte according to the specification of 2cm multiplied by 2cm, wherein the electroplating time is 10 min; the electroplated metallic nickel layer is used as a charge collection layer.
(3) Preparation of three-dimensional silicon structure/transition metal sulfide composite electrode material by high-temperature calcination method
(a) Electro-deposition nickel, cobalt hydroxide precursor
0.08mol/L nickel nitrate hexahydrate and 0.04mol/L cobalt nitrate hexahydrate were added to 30ml of deionized water. In a three-electrode system, a silicon wafer is used as a working electrode, Pt is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode for electrochemical deposition, the area of the silicon wafer entering an electrolyte is 1cm multiplied by 1cm, and the electrodeposition time is 300 s.
(b) Preparation of nickel-cobalt sulfide electrode material by high-temperature calcination method
Placing sublimed sulfur and nickel and cobalt hydroxide electrode materials into a crucible, placing the crucible into a horizontal tube furnace, and calcining at high temperature under the nitrogen atmosphere, wherein the sublimed sulfur is positioned at the upstream of the nickel-cobalt hydroxide electrode materials when a porcelain boat is placed. The temperature rise rate of the tube furnace was 10 ℃/min and maintained at 450 ℃ for 2 h.
Example 9
(1) And etching by a solution method to manufacture a three-dimensional silicon wafer, and carrying out secondary treatment on the three-dimensional silicon wafer.
(a) Selecting a metallurgical-grade silicon wafer, cutting the silicon wafer into 1cm by 2cm sample wafers, washing the sample wafers with isopropanol, and then carrying out reaction on concentrated sulfuric acid and hydrogen peroxide in a reaction condition of 3: 1 soaking in the solution for 20min, washing with deionized water, and spin-drying at high speed; and placing the silver nitrate into etching liquid containing 5mol/L and 0.02mol/L silver nitrate at normal temperature and normal pressure for etching for 60 min.
(b) And (3) soaking the silicon wafer in a concentrated nitric acid solution for more than 1h to remove residual silver particles on the surface of the silicon nanowire, fully cleaning the silicon wafer by using deionized water, and spin-drying the silicon wafer at a high speed by using a spin coater.
(c) Immersing the silicon wafer into a TMAH solution for secondary treatment for 1h to obtain a three-dimensional silicon wafer, wherein the treatment temperature is 20 ℃. Wherein the volume ratio of the TMAH solution to the isopropanol solution to the deionized water is 0.3:5: 25.
(2) Electroplating of metallic nickel layers
0.2mol/L of NiSO4·6H2O, 0.05mol/L NH4Cl and 0.025mol/L SDS. Under the bias voltage of 3V, taking a silicon wafer as a working electrode and Pt as a counter electrode, and stretching the silicon wafer into electrolyte according to the specification of 2cm multiplied by 2cm, wherein the electroplating time is 10 min; the electroplated metallic nickel layer is used as a charge collection layer.
(3) Preparation of three-dimensional silicon structure/transition metal selenide composite electrode material by high-temperature calcination method
(a) Electro-deposition nickel, cobalt hydroxide precursor
0.08mol/L nickel nitrate hexahydrate and 0.04mol/L cobalt nitrate hexahydrate were added to 30ml of deionized water. In a three-electrode system, a silicon wafer is used as a working electrode, Pt is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode for electrochemical deposition, the area of the silicon wafer entering an electrolyte is 1cm multiplied by 1cm, and the electrodeposition time is 300 s.
(b) High-temperature calcination method for preparing nickel selenide and cobalt electrode material
The selenium powder and the nickel cobalt hydroxide electrode material are put into a porcelain boat and put into a horizontal tube furnace to be calcined at high temperature under the nitrogen atmosphere, and the selenium powder is positioned at the upstream of the nickel cobalt hydroxide electrode material when the crucible is put. The temperature rise rate of the tube furnace was 10 ℃/min and maintained at 450 ℃ for 2 h.
Claims (10)
1. The three-dimensional silicon substrate/transition metal compound based composite electrode material is characterized in that a transition metal compound is prepared on the surface of a three-dimensional silicon substrate, the transition metal is one or more of transition metal materials such as nickel, cobalt, manganese, iron and the like, and the transition metal compound is a sulfide, a selenide or a mixture of the sulfide and the selenide of the transition metal compound.
2. The three-dimensional silicon matrix/transition metal compound based composite electrode material according to claim 1, further comprising a charge collection layer, wherein the charge collection layer is positioned between the three-dimensional silicon matrix and the transition metal compound layer to form a composite electrode material of a structure of "three-dimensional silicon matrix/charge collection layer/transition metal compound" or a composite electrode material of a structure of "three-dimensional silicon matrix/transition metal compound/charge collection layer" positioned on the upper part of the transition metal compound.
3. The three-dimensional silicon matrix/transition metal compound-based composite electrode material according to claim 2, wherein the charge collection layer is a conductive polymer, a carbon layer or a metal layer; the conductive polymer is prepared by an electrochemical method or a spin-coating method and is polypyrrole, polythiophene or polyaniline; the carbon layer is prepared by a spin coating method, a high-temperature calcination method or a hydrothermal method and is graphene, a conductive carbon layer or a carbon nano tube; the metal layer is prepared by a CVD method, an ALD method or an electrochemical method and is metallic nickel or TiN.
4. The method for preparing the three-dimensional silicon substrate/transition metal compound based composite electrode material as claimed in any one of claims 1 to 3, wherein the transition metal compound is prepared by an electrochemical method, and electrochemical deposition is carried out at a voltage of-1V by using a three-dimensional silicon substrate or a three-dimensional silicon substrate modified with a charge collection layer as a working electrode, Pt as a counter electrode and Ag/AgCl as a reference electrode; the electrolyte used for electrochemical deposition comprises transition metal salt and a sulfur source and/or a selenium source, or two electrolytes containing the transition metal salt and the sulfur source and the transition metal salt and the selenium source are alternately used for electrochemical deposition, and the electrodeposition time is 5-1200 s.
5. The method for preparing the three-dimensional silicon matrix/transition metal compound-based composite electrode material as claimed in claim 4, wherein the total concentration of the transition metal salt in the electrolyte is 0.02-0.2 mol/L, the content of the sulfur source is 1-6 times of that of the transition metal salt, and the content of the selenium source is 5-50% of that of the transition metal salt.
6. The method for preparing the three-dimensional silicon substrate/transition metal compound-based composite electrode material as claimed in any one of claims 1 to 3, wherein the transition metal compound is prepared by a hydrothermal method, namely, the three-dimensional silicon structure/transition metal hydroxide precursor is put into a solution containing a sulfur source or a selenium source for hydrothermal reaction.
7. The method for preparing the three-dimensional silicon substrate/transition metal compound-based composite electrode material according to any one of claims 1 to 3, wherein the transition metal compound is prepared by a high-temperature calcination method, namely, the three-dimensional silicon structure/transition metal hydroxide precursor is put into a high-temperature tube furnace, a sulfur source or a selenium source is put into the high-temperature tube furnace at the upstream, and high-temperature calcination is carried out in a nitrogen atmosphere to prepare the three-dimensional silicon structure/transition metal compound electrode material; wherein the heating rate of the high-temperature calcination is 2-8 ℃/min, the heat preservation temperature is 300-450 ℃, and the heat preservation time is 0.5-2.5 h.
8. The method for preparing a three-dimensional silicon substrate/transition metal compound-based composite electrode material according to claim 6 or 7, wherein the three-dimensional silicon structure/transition metal hydroxide precursor is prepared by a hydrothermal method or an electrochemical method comprising: firstly, taking a three-dimensional silicon substrate or the three-dimensional silicon substrate modified with a charge collection layer as a working electrode, Pt as a counter electrode and Ag/AgCl as a reference electrode, and carrying out electrochemical deposition for 10-500 s in an electrolyte containing transition metal salt and hexadecyl trimethyl ammonium bromide under the voltage of-1V to prepare a three-dimensional silicon substrate/transition metal hydroxide precursor; wherein the total concentration of the transition metal salt in the electrolyte is 0.08-0.15 mol/L.
9. The method for preparing the three-dimensional silicon matrix/transition metal compound-based composite electrode material according to any one of claims 4 to 7, wherein the sulfur source is one of thioacetamide, thiourea and sublimed sulfur; the selenium source is selenium dioxide and/or selenium powder.
10. The use of the three-dimensional silicon matrix/transition metal compound-based composite electrode material according to claim 2, wherein the composite electrode material of the "three-dimensional silicon matrix/transition metal compound/charge collection layer" structure is used as a energy storage electrode material and/or an energy conversion electrode material, and the prepared composite electrode material of the "three-dimensional silicon matrix/charge collection layer/transition metal compound" structure is used as an energy storage electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210232093.5A CN114649150A (en) | 2022-03-02 | 2022-03-02 | Three-dimensional silicon substrate/transition metal compound based composite electrode material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210232093.5A CN114649150A (en) | 2022-03-02 | 2022-03-02 | Three-dimensional silicon substrate/transition metal compound based composite electrode material, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114649150A true CN114649150A (en) | 2022-06-21 |
Family
ID=81994274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210232093.5A Pending CN114649150A (en) | 2022-03-02 | 2022-03-02 | Three-dimensional silicon substrate/transition metal compound based composite electrode material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114649150A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492452A (en) * | 2017-08-02 | 2017-12-19 | 河南师范大学 | The preparation method of array-like multilevel hierarchy cobalt sulfide nickel/nickel foam electrode of super capacitor |
| CN110610816A (en) * | 2019-09-18 | 2019-12-24 | 江苏大学 | Preparation method of carbon cloth-based nickel-cobalt double-metal selenide nano square sheet electrode material |
| CN111063548A (en) * | 2019-12-13 | 2020-04-24 | 江苏大学 | Three-dimensional silicon structure/polyaniline-based composite electrode material and preparation method thereof |
| CN111199835A (en) * | 2020-01-30 | 2020-05-26 | 浙江大学 | Preparation method of nickel cobalt selenium/nickel cobalt double hydroxide composite electrode material with hierarchical structure |
| CN111268744A (en) * | 2020-01-19 | 2020-06-12 | 北京辉腾格勒石墨烯科技有限公司 | Nickel-cobalt bimetallic sulfide and electrode preparation method thereof |
| CN111816453A (en) * | 2020-06-29 | 2020-10-23 | 江苏大学 | Three-dimensional silicon structure/nickel-cobalt hydroxide based composite electrode material and preparation method thereof |
| CN113012944A (en) * | 2021-02-24 | 2021-06-22 | 齐齐哈尔大学 | Preparation method and application of cobaltosic nickel tetrasulfide @ nickel vanadium double metal hydroxide composite material |
-
2022
- 2022-03-02 CN CN202210232093.5A patent/CN114649150A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492452A (en) * | 2017-08-02 | 2017-12-19 | 河南师范大学 | The preparation method of array-like multilevel hierarchy cobalt sulfide nickel/nickel foam electrode of super capacitor |
| CN110610816A (en) * | 2019-09-18 | 2019-12-24 | 江苏大学 | Preparation method of carbon cloth-based nickel-cobalt double-metal selenide nano square sheet electrode material |
| CN111063548A (en) * | 2019-12-13 | 2020-04-24 | 江苏大学 | Three-dimensional silicon structure/polyaniline-based composite electrode material and preparation method thereof |
| CN111268744A (en) * | 2020-01-19 | 2020-06-12 | 北京辉腾格勒石墨烯科技有限公司 | Nickel-cobalt bimetallic sulfide and electrode preparation method thereof |
| CN111199835A (en) * | 2020-01-30 | 2020-05-26 | 浙江大学 | Preparation method of nickel cobalt selenium/nickel cobalt double hydroxide composite electrode material with hierarchical structure |
| CN111816453A (en) * | 2020-06-29 | 2020-10-23 | 江苏大学 | Three-dimensional silicon structure/nickel-cobalt hydroxide based composite electrode material and preparation method thereof |
| CN113012944A (en) * | 2021-02-24 | 2021-06-22 | 齐齐哈尔大学 | Preparation method and application of cobaltosic nickel tetrasulfide @ nickel vanadium double metal hydroxide composite material |
Non-Patent Citations (1)
| Title |
|---|
| 黄克靖等: "《二维过渡金属二硫属化合物的电化学储能应用》", pages: 1 - 17 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xuan et al. | Hierarchical MnCo-LDH/rGO@ NiCo2S4 heterostructures on Ni foam with enhanced electrochemical properties for battery-supercapacitors | |
| Devaraj et al. | High capacitance of electrodeposited MnO2 by the effect of a surface-active agent | |
| Meng et al. | Synthesis of SnO2 nanoflowers and electrochemical properties of Ni/SnO2 nanoflowers in supercapacitor | |
| CN106876153B (en) | A kind of electrode of self supporting structure and its preparation and application | |
| CN106548877B (en) | Carbon nano pipe array/polyaniline/ceria composite electrode and its preparation method and application | |
| CN109616331B (en) | Core-shell type nickel hydroxide nanosheet/manganese cobalt oxide composite electrode material and preparation method thereof | |
| Li et al. | Hydrothermal synthesis and characterization of litchi-like NiCo2Se4@ carbon microspheres for asymmetric supercapacitors with high energy density | |
| CN107768600B (en) | A kind of foam copper base lithium ion cell negative electrode material and preparation method thereof | |
| Yuan et al. | Cu-doped NiO for aqueous asymmetric electrochemical capacitors | |
| CN110993368A (en) | Composite electrode material, preparation method and super capacitor | |
| Nakayama et al. | Direct growth of birnessite-type MnO2 on treated carbon cloth for a flexible asymmetric supercapacitor with excellent cycling stability | |
| Wan et al. | Three-dimensional cotton-like nickel nanowire@ Ni–Co hydroxide nanosheet arrays as binder-free electrode for high-performance asymmetric supercapacitor | |
| Zhang et al. | Mild synthesis route to nanostructured α-MnO2 as electrode materials for electrochemical energy storage | |
| CN108987688B (en) | Carbon-based composite material, preparation method and sodium ion battery | |
| CN108630449B (en) | Flexible asymmetric super capacitor with ultrahigh energy density and preparation method thereof | |
| Kang et al. | Simple fabrication of nickel sulfide nanostructured electrode using alternate dip-coating method and its supercapacitive properties | |
| Chen et al. | High-performanced flexible solid supercapacitor based on the hierarchical MnCo2O4 micro-flower | |
| Raza et al. | Metal oxide-conducting polymer-based composite electrodes for energy storage applications | |
| Luo et al. | An ultra-thin interlayer bimetallic sulfide for enhancing electrons transport of supercapacitor electrode | |
| KR20190024332A (en) | An electrode material in which metal carbide nanoparticles are deposited on a three-dimensional carbon flower structure and The super capacitor electrode | |
| Shen et al. | A novel 3D porous electrode of polyaniline and PEDOT: PSS coated SiNWs for low-cost and high-performance supercapacitors | |
| Min et al. | Porous nanosheet–nanosphere@ nanosheet FeNi 2-LDH@ FeNi 2 S 4 core–shell heterostructures for asymmetric supercapacitors | |
| CN114649150A (en) | Three-dimensional silicon substrate/transition metal compound based composite electrode material, preparation method and application | |
| CN112768258B (en) | Polyaniline-loaded aluminum-doped manganese dioxide @ carbon cloth-based flexible supercapacitor electrode material and preparation method and application thereof | |
| US9147529B2 (en) | Energy storage device and method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |