CN112992555A - Electrode with residual ions, preparation and application - Google Patents
Electrode with residual ions, preparation and application Download PDFInfo
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- CN112992555A CN112992555A CN201911283193.5A CN201911283193A CN112992555A CN 112992555 A CN112992555 A CN 112992555A CN 201911283193 A CN201911283193 A CN 201911283193A CN 112992555 A CN112992555 A CN 112992555A
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- ions
- electrode
- ion
- electrolyte
- working electrode
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- 150000002500 ions Chemical class 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 75
- 150000001450 anions Chemical class 0.000 claims abstract description 48
- 150000001768 cations Chemical class 0.000 claims abstract description 45
- 239000013543 active substance Substances 0.000 claims abstract description 44
- 239000004020 conductor Substances 0.000 claims abstract description 6
- 239000011532 electronic conductor Substances 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims abstract 2
- -1 hydrogen ions Chemical class 0.000 claims description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 44
- 229910001416 lithium ion Inorganic materials 0.000 claims description 44
- 229910001415 sodium ion Inorganic materials 0.000 claims description 43
- 229910021385 hard carbon Inorganic materials 0.000 claims description 40
- 239000003990 capacitor Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 30
- 229910021645 metal ion Inorganic materials 0.000 claims description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 27
- 230000005684 electric field Effects 0.000 claims description 24
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 15
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 230000001276 controlling effect Effects 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910021384 soft carbon Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007784 solid electrolyte Substances 0.000 claims description 7
- 238000012983 electrochemical energy storage Methods 0.000 claims description 6
- 239000011245 gel electrolyte Substances 0.000 claims description 5
- 239000011244 liquid electrolyte Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001449 anionic compounds Chemical class 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 150000001767 cationic compounds Chemical class 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 4
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002891 organic anions Chemical class 0.000 claims description 4
- 150000002892 organic cations Chemical class 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims description 4
- MJEPCYMIBBLUCJ-UHFFFAOYSA-K sodium titanium(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Na+] MJEPCYMIBBLUCJ-UHFFFAOYSA-K 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004966 Carbon aerogel Substances 0.000 claims description 2
- 239000006245 Carbon black Super-P Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 102000004310 Ion Channels Human genes 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000002223 garnet Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910001449 indium ion Inorganic materials 0.000 claims description 2
- 229910021432 inorganic complex Inorganic materials 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000005837 radical ions Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229940124530 sulfonamide Drugs 0.000 claims description 2
- 229910001432 tin ion Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000006258 conductive agent Substances 0.000 description 40
- 239000011230 binding agent Substances 0.000 description 21
- 239000000853 adhesive Substances 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 19
- 230000002427 irreversible effect Effects 0.000 description 14
- 238000007600 charging Methods 0.000 description 12
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 239000005022 packaging material Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 10
- 239000012982 microporous membrane Substances 0.000 description 10
- 239000002985 plastic film Substances 0.000 description 10
- 229920006255 plastic film Polymers 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010280 constant potential charging Methods 0.000 description 8
- 238000007606 doctor blade method Methods 0.000 description 8
- 229910001290 LiPF6 Inorganic materials 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910019398 NaPF6 Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000010277 constant-current charging Methods 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 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 2
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical group P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the field of electrochemistry, and particularly relates to an electrode with residual ions, and preparation and application thereof, wherein the constituent substances of the electrode comprise an electronic conductor, an active substance and an electrolyte attached to the electronic conductor and the active substance; residual electrons or residual holes are simultaneously carried in the electrodes, and cations and anions are introduced by the electrolyte; wherein the remaining electrons or holes are present on the electron conductor and/or the active substance, and anions and cations are present in the electrolyte; the absolute values of the charges carried by the anions and the cations in the electrolyte are not equal; when the electrode has residual electrons, the net charge amount is NResidual electronsThe total charge of the cations attached to the electrode is greater than the total charge of the anions, the net charge of the ions is positive, and the net charge of the cations is MCation(s)(ii) a When the electrode has residual holes, the net charge amount is NResidual cavityThe total charge of the cations on the electrode is less than that of the anions, the net charge of the ions is negative, and the net charge of the anions is MAnion(s)。
Description
Technical Field
The invention belongs to the field of electrochemistry and chemistry, and particularly relates to an electrode with residual ions, a preparation method and application.
Technical Field
Currently, electrodes are widely used in the electrochemical and chemical fields. However, the electrodes used in electrochemical devices and chemical processes do not have residual charges, residual holes, and residual ions, and the electrode potential can be adjusted only once by an external electric field, so the adjusting effect is limited.
If the electrode is subjected to charge modulation in advance to enable the electrode to have residual charges (or residual holes) and residual ions, the electrode potential and the surface interface property of the electrode at the initial stage of application can be changed, and a brand-new effect is brought to a reaction system where the electrode is located.
For metal ion batteries, especially lithium ion batteries and sodium ion batteries, the problem of low first pass of the negative electrode material is one of the most major problems in the application. In the first cycle, the negative electrode material forms an SEI film at the interface to consume lithium ions extracted from the positive electrode, and the irreversible capacity causes low utilization rate of the positive electrode active material and reduces the capacity and energy density of the battery. To solve this problem, for example, lithium ion batteries are often manufactured by a method of forming a negative electrode in advance, a method of spraying lithium powder on a negative electrode, a method of making a positive electrode rich in lithium, and the like. The methods can solve the problem of irreversible capacity of the cathode material, but lithium metal and other lithium-rich materials are required to be used, or low-potential high-reactivity metal pre-embedded cathodes are detached, so that the cost is high, the process is complex, and potential safety hazards exist, so that the search for a proper and reliable pre-embedded lithium technology is a recognized technical difficulty and is also an urgent need for the development of lithium ion batteries, and the same problem exists for other types of metal ion batteries.
Disclosure of Invention
The invention proposes an electrode which, when present alone, carries residual electrons or residual holes, and which, when present alone, carries an electric double layer based on residual anions or residual cations. The oxidation-reduction potential and the interface reaction characteristic of the electrode can be continuously adjusted by regulating the content of the residual charges. The electrode can be applied to the fields of electrochemical energy storage, electrochemical synthesis, chemical synthesis, wastewater treatment and the like, and has excellent effects.
The electrode is composed of an electron conductor, an active material, and an attached electrolyte. The electrode carries both residual electrons (or residual holes), cations and anions. Wherein free electrons or holes are present on the electrode and anions and cations are present in the electrolyte. Wherein the sum of the charges of the anion and the cation is not zero.
When the electrode carries residual electrons (with a net charge of N)Residual electrons) The total charge of the cations attached to the electrodes is greater than the total charge of the anions, and the net charge of the ions is positive (the net charge is M)Cation(s)). When the electrode has residual holes (with a net charge of N)Residual cavity) The total charge of the cations on the electrode is less than that of the anions, and the net charge of the ions is negative (the net charge of the ions is M)Anion(s))。
The residual electrons and ions on the electrode can stably coexist. Total amount of remaining electrons or remaining holes NResidual electronsAnd NResidual cavityCan be regulated and controlled, and the apparent charge density of the residual electrons and the residual holes is 0.01C/cm2～100C/cm2。
There is a ratio between the total amount of remaining electrons on the electrode and the total amount of electrostatic charge of the attached ions, which may be in the range of NResidual electrons：MCation(s)1: 2-2: 1. The proportion of charges can be achieved by quantitatively increasing or decreasing a portion of electrons or holes. The method for increasing or decreasing the electron or the hole comprises one or more than two of the following steps: 1) contacting an object with electrons or holes with an electrode to transfer the electrons or holes, 2) leading part of the electrons or holes away by a lead, and 3) contacting other objects with anions and cations with the electrode to transfer the ions.
The ion species are inorganic cation, inorganic anion, organic cation, organic anion, ionic complex and ionic complex. Preferably, the inorganic cations include: hydrogen ions, organic amine ions, ammonium ions, potassium ions, sodium ions, calcium ions, magnesium ions, aluminum ions, zinc ions, iron ions, tin ions, lead ions, bismuth ions, mercury ions, silver ions, gold ions, platinum ions, palladium ions, iridium ions, indium ions, titanium ions, vanadium ions, chromium ions, manganese ions, cobalt ions, nickel ions, copper ions, niobium ions, zirconium ions, and hydrated ions of the foregoing ions, and organic complex ions of the foregoing ions, and inorganic complex ions containing the foregoing metal ions. Preferably, the inorganic anions include: a hydroxide ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a sulfide ion, a silicon ion, a nitrogen ion, a phosphate ion, an arsenic ion, a carbonate ion, a nitrate ion, and a hydrate ion of the above ions, and an organic complex ion of the above ions, and an oxygen acid radical ion containing the above ion element, and a metal complex ion containing the above ion element. Preferably, the organic cations include: primary amine ions, secondary amine ions, tertiary amine ions, quaternary amine ions, organophosphorus ions, imidazole cations, pyridine cations, sulfonimide ions, sulfonamide ions, and derivatives of the foregoing ions. Preferably, the organic anions include: organic sulfonic acid ions, organic phosphoric acid ions, organic boric acid ions, oxalic acid ions, carbonic acid ions, acetic acid ions, and derivatives of the foregoing ions. The ions may be present in the liquid electrolyte at the surface of the electrode, or may be present in the solid or gel electrolyte at the surface of the electrode.
The electronic conductor is one or more than two of commercialized carbon nano-tube, graphene, carbon nano-fiber, BP2000, KB600, KB300, XC-72, Super-P, acetylene black and active carbon.
The active substance is one or more than two of active carbon, carbon fiber, carbon nano tube, graphite and carbon aerogel.
The electrolyte can be one or more of liquid electrolyte, solid electrolyte or gel electrolyte. The liquid electrolyte solute is the salt of the anion and the cation, and the solvent is one or more than two of Polycarbonate (PC), Ethylene Carbonate (EC) and diethyl carbonate (DEC). The solid electrolyte is a mixture of the salt of the anion and the cation and polyethylene oxide (PEO) polymer or a garnet solid electrolyte. The gel electrolyte solute is the anion and cation salt, and the gel polymer is one or more of polyethylene oxide (PEO), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polymethyl methacrylate (PMMA) and polyvinyl acetal (PVB/PVFM).
The preparation method of the electrode comprises the following steps: 1) filling electrolyte between the two electrodes, applying an electric field on the two electrodes to transfer electrons between the two electrodes, and in the process, directionally transferring anions and cations in the electrolyte to the two electrodes respectively and achieving balance; 2) controlling the total amount of ions transferred between the two electrodes by controlling the electric field intensity and the electric field time; 3) and quickly cutting off an ion transmission channel between the two electrodes to obtain the electrodes with different total amounts of anions and cations. After the ion channel is cut off, two charged electrodes are obtained simultaneously, and the two charged electrodes are respectively provided with residual electrons and residual holes. Wherein the absolute value of the charge of the anion and the charge of the cation which are carried by each electrode are not equal.
The electrochemical energy storage device is used for electrochemical energy storage and comprises one of a lithium ion super capacitor, a sodium ion super capacitor and a metal ion battery, wherein the metal ion is one of sodium ion, magnesium ion, potassium ion, calcium ion or aluminum ion.
The electrochemical energy storage device consists of a positive electrode, a negative electrode, a diaphragm, an electrolyte and a packaging material; wherein the electrolyte is in a solid, liquid or colloidal state;
the application of the electrode in the lithium ion super capacitor comprises the following specific processes: 1) contacting a working electrode containing an activated carbon material with an electrolyte capable of conducting lithium ions, the other side of the electrolyte being in contact with a counter electrode; 2) applying an electric field between the working electrode and the counter electrode: when the electrons are gathered to one side of the working electrode, lithium ions are gathered to one side of the working electrode, and an electric double layer is formed at the interface of the working electrode, wherein the content of the lithium ions in the electric double layer exceeds the total charge carried by anions; 3) the proportion and the content of lithium ions in the double electric layers are regulated and controlled by controlling the time of the action of the electric field; 4) separating the working electrode from the electrolyte body, the working electrode being provided with an electric double layer; 5) the working electrode is used as the positive electrode of the lithium ion super capacitor, and the working electrode, the electrolyte and the new negative electrode form a new hybrid super capacitor, and the active substance of the new negative electrode is one or more than two of lithium titanate, hard carbon, soft carbon, silicon, niobium oxide and graphite;
or, the application of the electrode in the sodium ion super capacitor is as follows: 1) contacting a working electrode containing an activated carbon material with an electrolyte capable of conducting sodium ions, the other side of the electrolyte being in contact with a counter electrode; 2) applying an electric field between the working electrode and the counter electrode: when the electrons are gathered to one side of the working electrode, sodium ions are gathered to one side of the working electrode, and an electric double layer is formed at the interface of the working electrode, wherein the content of the sodium ions in the electric double layer exceeds the total charge carried by anions; 3) the proportion and the content of sodium ions in the double electric layers are regulated and controlled by controlling the time of the action of the electric field; 4) separating the working electrode from the electrolyte body, the working electrode being provided with an electric double layer; 5) the working electrode is used as the positive electrode of the sodium ion super capacitor, and forms a new mixed super capacitor with electrolyte and a new negative electrode, and the active substance of the new negative electrode is one or more than two of sodium titanate, hard carbon, soft carbon, sodium titanium phosphate and graphite;
or, the application of the electrode in the metal ion battery is as follows: 1) contacting a working electrode comprising a metal ion releasable material with an electrolyte capable of conducting metal ions, the other side of the electrolyte being in contact with a counter electrode; 2) applying an electric field between the working electrode and the counter electrode: when the electrons are gathered to one side of the working electrode, metal ions are gathered to one side of the working electrode, and an electric double layer is formed at the interface of the working electrode, wherein the content of the metal ions in the electric double layer exceeds the total charge carried by anions; 3) the proportion and the content of metal ions in the double electric layers are regulated and controlled by controlling the time of the action of the electric field; 4) separating the working electrode from the electrolyte body, wherein the working electrode is provided with an electric double layer with excessive metal ions; 5) the working electrode is used as the positive electrode of the metal ion battery, and forms new metal ions with the electrolyte and the new negative electrode, the active substance of the new negative electrode is one or more than two of hard carbon, soft carbon or graphite, the active substance of the new negative electrode can also be lithium titanate in the case of the lithium ion battery, and the active substance of the new negative electrode can also be sodium titanate and sodium titanium phosphate in the case of the sodium ion battery.
The invention has the beneficial effects that:
1) in a lithium ion super capacitor or a sodium ion super capacitor, an electrode with residual lithium ions or sodium ions in advance can be used as a positive electrode, and graphite, soft carbon or hard carbon materials of a negative electrode are pre-embedded with lithium or sodium, so that the energy storage energy density of the device is greatly improved. The improvement amplitude can reach more than 50%.
2) In the metal ion super battery, an electrode with residual technical ions can be used as a positive electrode, and metal is pre-embedded in graphite, soft carbon or hard carbon materials of a negative electrode, so that the energy storage energy density of the device is greatly improved. The improvement amplitude can reach more than 20%.
Drawings
Fig. 1, schematic of an electrode containing residual ions (left figure is an electrode with residual anions, right figure is an electrode with residual cations).
Detailed Description
Example 1:
preparation of lithium ion super capacitor
The working electrode was first prepared by a doctor blade method. The working electrode material comprises the following components of active substances, a binder and a conductive agent, wherein the active substances: adhesive: the mass ratio of the conductive agent is 95: 2: 3. the active substance is active carbon, the binder is PVDF, and the conductive agent is carbon nano tubes. The working electrode and the counter electrode were placed on both sides of the electrolyte. The composition of the counter electrode is the same as the working electrode. The electrolyte used is LiPF6Propylene carbonate solution with a content of 1M. And applying electric fields on the working electrode and the counter electrode, and discharging in a constant-current and constant-voltage mode. The current is constant at 1mA/cm2The cut-off voltage was 1.0V. During discharge, lithium ions (Li)+) Hexafluorophosphate radical (PF) enrichment at working electrode interface6 -) Enrichment at the interface of the counter electrode.
And after the discharge is finished, taking out the working electrode for preparing the lithium ion super capacitor. The super capacitor consists of a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and a shell. Wherein the positive electrode is prepared working electrode with residual electrons and net charge amount of NResidual electronsThe total charge of the cations attached to the electrode is greater than the total charge of the anions, the net charge of the ions is positive, and the net charge of the cations is MCation(s)The working electrode N: the ratio of M is 1:1, and the apparent charge density of the remaining electrons is 0.4C/cm2. The negative electrode is made of hard carbon: conductive agent: binder 95: 3: 2, coating on a copper foil with the thickness of 8 um. The capacity ratio of the active material of the positive electrode to the negative electrode was 1: 2. the diaphragm is
A microporous membrane. The electrolyte is LiPF6A solution of propylene carbonate with a content of 1M. The packaging material is an aluminum plastic film.
The prepared lithium ion super capacitor is charged in a constant-current and constant-voltage charging mode, the charging cut-off voltage is 4.35V, and the cut-off current is 0.1mA/cm2. In the process, lithium ions enriched on the working electrode interface are embedded into the hard carbon to make up the irreversible loss of the hard carbon cathode in the first charge-discharge process. Then the lithium ion super capacitor can be smoothly charged and discharged.
Comparative example 1:
preparation of lithium ion super capacitor
The working electrode was first prepared by a doctor blade method. The components of the electrode material are active substance, adhesive and conductive agent, and the ratio of active substance: adhesive: the mass ratio of the conductive agent is 95: 2: 3. the active substance is active carbon, the binder is PVDF, and the conductive agent is carbon nano tubes. The lithium ion super capacitor consists of a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and a shell. Wherein, the positive electrode is the prepared working electrode. The negative electrode is made of hard carbon: conductive agent: binder 95: 3: 2 of the materialComposition, coated on a copper foil 8um thick. The diaphragm is
A microporous membrane. The electrolyte is LiPF6A solution of propylene carbonate with a content of 1M. The packaging material is an aluminum plastic film.
The prepared lithium ion super capacitor adopts a constant-current-first and constant-voltage charging mode, the charging cut-off voltage is 4.35V, and the cut-off current is 0.1mA/cm2. In the process, no redundant lithium ions at the interface of the working electrode are inserted into the hard carbon, so that the irreversible loss of the hard carbon negative electrode in the first charge-discharge process cannot be compensated.
Example 2:
preparation of lithium ion batteries
The working electrode was first prepared by a doctor blade method. The components of the electrode material are active substance, adhesive, additive and conductive agent, and the ratio of active substance: adhesive: additive: the mass ratio of the conductive agent is 95: 2: 1: 2. the active material is lithium iron phosphate, the binder is PVDF, and the conductive agent is a carbon nano tube. The working electrode and the counter electrode were placed on both sides of the electrolyte. The composition of the counter electrode was metallic lithium. The electrolyte used is LiPF6A solution of propylene carbonate with a content of 1M. And applying electric fields on the working electrode and the counter electrode, and discharging in a constant-current and constant-voltage mode. The current is constant at 1mA/cm2The cut-off voltage was 1.0V. During discharge, lithium ions (Li)+) Enrichment at the working electrode interface.
And after the discharge is finished, taking out the working electrode for preparing the lithium ion battery. The lithium ion battery consists of a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and a shell. Wherein the positive electrode is prepared working electrode with residual electrons and net charge amount of NResidual electronsThe total charge of the cations attached to the electrode is greater than the total charge of the anions, the net charge of the ions is positive, and the net charge of the cations is MCation(s)The working electrode N: the ratio of M is 1:1, and the apparent charge density of the remaining electrons is 0.4C/cm2. The negative electrode is made of hard carbon: conductive agent: binder 95: 3:2, coating on a copper foil with the thickness of 8 um. The diaphragm is
A microporous membrane. The electrolyte is LiPF6A solution of propylene carbonate with a content of 1M. The packaging material is an aluminum plastic film.
The prepared lithium ion battery adopts a constant-current and constant-voltage charging mode, the charging cut-off voltage is 4.2V, and the cut-off current is 0.1mA/cm2. In the process, lithium ions enriched on the working electrode interface are embedded into the hard carbon to make up the irreversible loss of the hard carbon cathode in the first charge-discharge process. The lithium ion battery can then be charged and discharged at 100% DOD at a rate of 1C.
Comparative example 2:
preparation of lithium ion batteries
The working electrode was first prepared by a doctor blade method. The components of the electrode material are active substance, adhesive and conductive agent, and the ratio of active substance: adhesive: the mass ratio of the conductive agent is 95: 2: 3. the active material is lithium iron phosphate, the binder is PVDF, and the conductive agent is a carbon nano tube. The lithium ion battery consists of a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and a shell. Wherein, the positive electrode is the prepared working electrode. The negative electrode is made of hard carbon: conductive agent: binder 95: 3: 2, coating on a copper foil with the thickness of 8 um. The diaphragm is
A microporous membrane. The electrolyte is LiPF6A solution of propylene carbonate with a content of 1M. The packaging material is an aluminum plastic film.
The prepared lithium ion battery adopts a constant-current and constant-voltage charging mode, the charging cut-off voltage is 4.2V, and the cut-off current is 0.1mA/cm2. In the process, no redundant lithium ions at the interface of the working electrode are inserted into the hard carbon, so that the irreversible loss of the hard carbon negative electrode in the first charge-discharge process cannot be compensated.
Example 3:
preparation of sodium ion battery
Firstly adopting a blade coating methodAnd preparing a working electrode. The components of the electrode material are active substance, adhesive, additive and conductive agent, and the ratio of active substance: adhesive: additive: the mass ratio of the conductive agent is 95: 2: 1: 2. the active substance is sodium vanadium fluorophosphate, the binder is PVDF, and the conductive agent is a carbon nano tube. The working electrode and the counter electrode were placed on both sides of the electrolyte. The composition of the counter electrode is metallic sodium. The electrolyte used is NaPF6A solution of propylene carbonate with a content of 1M. And applying electric fields on the working electrode and the counter electrode, and discharging in a constant-current and constant-voltage mode. The current is constant at 1mA/cm2The cut-off voltage was 1.0V. During discharge, sodium ions (Na)+) Enrichment at the working electrode interface.
And after the discharge is finished, taking out the working electrode for preparing the sodium-ion battery. The sodium ion battery consists of a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and a shell. Wherein the positive electrode is prepared working electrode with residual electrons and net charge amount of NResidual electronsThe total charge of the cations attached to the electrode is greater than the total charge of the anions, the net charge of the ions is positive, and the net charge of the cations is MCation(s)The working electrode N: the ratio of M is 1:1, and the apparent charge density of the remaining electrons is 0.4C/cm2. The negative electrode is made of hard carbon: conductive agent: binder 95: 3: 2, coating on a copper foil with the thickness of 8 um. The diaphragm is
A microporous membrane. The electrolyte is NaPF6A solution of propylene carbonate with a content of 1M. The packaging material is an aluminum plastic film.
The prepared sodium ion super capacitor adopts a constant-current-first constant-voltage charging mode, the charging cut-off voltage is 4.3V, and the cut-off current is 0.1mA/cm2. In the process, lithium ions enriched on the working electrode interface are embedded into the hard carbon, so that irreversible loss generated in the first charge-discharge process of the hard carbon cathode is compensated. The sodium ion battery can then be charged and discharged at 100% DOD at a rate of 1C.
Comparative example 3:
preparation of sodium ion battery
The working electrode was first prepared by a doctor blade method. The components of the electrode material are active substance, adhesive, additive and conductive agent, and the ratio of active substance: adhesive: additive: the mass ratio of the conductive agent is 95: 2: 1: 2. the active substance is sodium vanadium fluorophosphate, the binder is PVDF, and the conductive agent is a carbon nano tube. The sodium ion battery consists of a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and a shell. Wherein, the positive electrode is the prepared working electrode. The negative electrode is made of hard carbon: conductive agent: binder 95: 3: 2, coating on a copper foil with the thickness of 8 um. The diaphragm is
A microporous membrane. The electrolyte is NaPF6A solution of propylene carbonate with a content of 1M. The packaging material is an aluminum plastic film.
The prepared sodium ion battery adopts a constant-current and constant-voltage charging mode, the charging cut-off voltage is 4.3V, and the cut-off current is 0.1mA/cm2. In the process, no redundant sodium ions are embedded into the hard carbon at the interface of the working electrode, so that the irreversible loss of the hard carbon cathode in the first charge-discharge process cannot be compensated.
Example 4:
preparation of magnesium ion battery
The working electrode was first prepared by a doctor blade method. The components of the electrode material are active substance, adhesive, additive and conductive agent, and the ratio of active substance: adhesive: additive: the mass ratio of the conductive agent is 95: 2: 1: 2. the active substance is vanadium pentoxide, the binder is PVDF, and the conductive agent is carbon nano tubes. The working electrode and the counter electrode were placed on both sides of the electrolyte. The composition of the counter electrode is metal magnesium. The electrolyte used was a solution of Mg (AlCl2BuEt)2 in 1M tetrahydrofuran. And applying electric fields on the working electrode and the counter electrode, and discharging in a constant-current and constant-voltage mode. The current is constant at 1mA/cm2The cut-off voltage was 1.0V. During discharge, magnesium ions (Mg)+) Enrichment at the working electrode interface.
After the discharge is finished, taking out the working electrode for preparing the magnesium ion battery. The magnesium ion battery consists of a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and a shell. Wherein the positive electrode is prepared working electrode with residual electrons and net charge amount of NResidual electronsThe total charge of the cations attached to the electrode is greater than the total charge of the anions, the net charge of the ions is positive, and the net charge of the cations is MCation(s)The working electrode N: the ratio of M is 1:1, and the apparent charge density of the remaining electrons is 0.4C/cm2. The negative electrode is made of hard carbon: conductive agent: binder 95: 3: 2, coating on a copper foil with the thickness of 8 um. The diaphragm is
A microporous membrane. The electrolyte used was a solution of Mg (AlCl2BuEt)2 in 1M tetrahydrofuran. The packaging material is an aluminum plastic film.
The prepared magnesium ion battery adopts a constant-current-first and constant-voltage-second charging mode, the charging cut-off voltage is 1.6V, and the cut-off current is 0.1mA/cm2. In the process, magnesium ions enriched on the working electrode interface are embedded into the hard carbon to make up the irreversible loss generated in the first charge-discharge process of the hard carbon cathode. The magnesium ion battery can then be charged and discharged at 100% DOD at a rate of 1C.
Comparative example 4
Magnesium ion battery
The magnesium ion battery consists of a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and a shell. The anode is prepared by adopting a blade coating method, the components of the electrode material are active substances, adhesives, additives and conductive agents, and the active substances are as follows: adhesive: additive: the mass ratio of the conductive agent is 95: 2: 1: 2, the active substance is vanadium pentoxide, the binder is PVDF, and the conductive agent is carbon nano tube. The negative electrode is made of hard carbon: conductive agent: binder 95: 3: 2, coating on a copper foil with the thickness of 8 um. The diaphragm is
A microporous membrane. The electrolyte used was a solution of Mg (AlCl2BuEt)2 in 1M tetrahydrofuran. The packaging material is aluminumAnd (5) plastic film forming.
The prepared magnesium ion battery adopts a constant-current-first and constant-voltage-second charging mode, the charging cut-off voltage is 1.6V, and the cut-off current is 0.1mA/cm2. In the process, no redundant magnesium ions are embedded into the hard carbon at the interface of the working electrode, so that the irreversible loss of the hard carbon cathode in the first charge-discharge process cannot be compensated.
Example 5:
preparation of sodium ion super capacitor
The working electrode was first prepared by a doctor blade method. The components of the electrode material are active substance, adhesive and conductive agent, and the ratio of active substance: adhesive: the mass ratio of the conductive agent is 95: 2: 3. the active substance is active carbon, the binder is PVDF, and the conductive agent is carbon nano tubes. The working electrode and the counter electrode were placed on both sides of the electrolyte. The composition of the counter electrode is the same as the working electrode. The electrolyte used is LiPF6A solution of propylene carbonate with a content of 1M. And applying electric fields on the working electrode and the counter electrode, and discharging in a constant-current and constant-voltage mode. The current is constant at 1mA/cm2The cut-off voltage was 1.0V. During discharge, sodium ions (Na)+) Hexafluorophosphate radical (PF) enrichment at working electrode interface6 -) Enrichment at the interface of the counter electrode.
And after the discharge is finished, taking out the working electrode for preparing the sodium ion super capacitor. The super capacitor consists of a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and a shell. Wherein the positive electrode is prepared working electrode with residual electrons and net charge amount of NResidual electronsThe total charge of the cations attached to the electrode is greater than the total charge of the anions, the net charge of the ions is positive, and the net charge of the cations is MCation(s)The working electrode N: the ratio of M is 1:1, and the apparent charge density of the remaining electrons is 0.4C/cm2. The negative electrode is made of hard carbon: conductive agent: binder 95: 3: 2, coating on a copper foil with the thickness of 8 um. The capacity ratio of the active material of the positive electrode to the negative electrode was 1: 2. the diaphragm is
A microporous membrane. The electrolyte is NaPF6A solution of propylene carbonate with a content of 1M. The packaging material is an aluminum plastic film.
The prepared sodium ion super capacitor adopts a constant-current-first constant-voltage charging mode, the charging cut-off voltage is 2.0V, and the cut-off current is 0.1mA/cm2. In the process, sodium ions enriched on the working electrode interface are embedded into the hard carbon to make up the irreversible loss of the hard carbon cathode in the first charge-discharge process. Then the sodium ion hybrid super capacitor can be smoothly charged and discharged.
Comparative example 5:
preparation of sodium ion super capacitor
The working electrode was first prepared by a doctor blade method. The components of the electrode material are active substance, adhesive and conductive agent, and the ratio of active substance: adhesive: the mass ratio of the conductive agent is 95: 2: 3. the active substance is active carbon, the binder is PVDF, and the conductive agent is carbon nano tubes. The sodium ion mixed super capacitor comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and a shell. Wherein, the positive electrode is the prepared working electrode. The negative electrode is made of hard carbon: conductive agent: binder 95: 3: 2, coating on a copper foil with the thickness of 8 um. The capacity ratio of the active material of the positive electrode to the negative electrode was 1: 2. the diaphragm is
A microporous membrane. The electrolyte is NaPF6A solution of propylene carbonate with a content of 1M. The packaging material is an aluminum plastic film.
The prepared sodium ion super capacitor adopts a constant-current-first constant-voltage charging mode, the charging cut-off voltage is 2.0V, and the cut-off current is 0.1mA/cm2. In the process, no redundant sodium ions are embedded into the hard carbon at the interface of the working electrode, so that the irreversible loss of the hard carbon cathode in the first charge-discharge process cannot be compensated.
From the battery performance comparison in tables 1-5, it can be seen that the application of the electrode with residual ions in the battery improves the first coulombic efficiency of the battery from 70% to 99%, eliminates the influence of the irreversible capacity of the hard carbon first ring on the battery, and greatly improves the capacity exertion and capacity retention rate of the positive electrode. The irreversible capacity of the first circle of the negative electrode material is made up by utilizing the ions enriched on the surface of the working electrode, the first coulombic efficiency of the battery is obviously improved, the working potential of the hard carbon negative electrode is reduced, the ideal working voltage window selection is realized, the reversible specific capacity of the battery is improved, and the energy storage energy density of the device is greatly improved. The electrode with the residual ions is used for realizing the pre-embedding of the metal ions, the addition of active metal or metal-rich materials is reduced compared with the traditional metal pre-embedding mode, only the working electrode with lower reaction activity and the residual ions needs to be detached for assembling the battery, the safety is better, and the process is simple. Meanwhile, the apparent charge density of the residual ions on the working electrode can be regulated and controlled by changing the cut-off voltage, the regulation and control are easy, the diversified requirements of different types of energy storage devices can be met, and the application prospect is wide.
TABLE 1
| First coulombic efficiency | Reversible specific capacity of positive electrode | |
| Example 1 | 99％ | 35mAh/g |
| Comparative example 1 | 75％ | 15mAh/g |
TABLE 2
| First coulombic efficiency | Reversible specific capacity of positive electrode | |
| Example 2 | 99％ | 160mAh/g |
| Comparative example 2 | 70％ | 100mAh/g |
TABLE 3
| First coulombic efficiency | Reversible specific capacity of positive electrode | |
| Example 3 | 99％ | 130mAh/g |
| Comparative example 3 | 70％ | 60mAh/g |
TABLE 4
TABLE 5
| Capacity retention at-40 ℃ C | Capacity retention at-30 ℃ C | |
| Example 5 | 60％ | 80％ |
| Comparative example 5 | 30％ | 50％ |
Claims (10)
1. An electrode with residual ions, characterized in that:
the constituent materials of the electrode include an electron conductor and an active material, and an electrolyte attached thereto; residual electrons or residual holes are simultaneously carried in the electrodes, and cations and anions are introduced by the electrolyte; wherein the remaining electrons or holes are present on the electron conductor and/or the active substance, and anions and cations are present in the electrolyte;
the absolute values of the charges carried by the anions and the cations in the electrolyte are not equal;
when the electrode has residual electrons, the net charge amount is NResidual electronsThe total charge of the cations attached to the electrode is greater than the total charge of the anions, the net charge of the ions is positive, and the net charge of the cations is MCation(s)；
When the electrode has residual holes, the net charge amount is NResidual cavityThe total charge of the cations on the electrode is less than that of the anions, the net charge of the ions is negative, and the net charge of the anions is MAnion(s)。
2. The electrode of claim 1, wherein:
the residual electrons or residual holes on the electrode can stably coexist with the cations and the anions; total amount of remaining electrons or remaining holes NResidual electronsOr NResidual cavityCan be regulated and controlled, and the apparent charge density of the residual electrons or the residual holes is 0.01C/cm2～100C/cm2。
3. The electrode of claim 1, wherein:
there is a certain ratio between the total amount of remaining electrons or remaining holes N on the electrode and the total amount of net charge M attached to the anions and cations, where N: m is 1: 2-2: 1, regulating and controlling; the ratio of N to M can be achieved by quantitatively increasing or decreasing a part of electrons or holes.
4. The electrode of claim 3, wherein the means for increasing or decreasing the number of electrons or holes comprises one or more of: 1) contacting an object with electrons or holes with an electrode to transfer the electrons or holes, 2) leading part of the electrons or holes away by a lead, and 3) contacting other objects with anions and cations with the electrode to transfer the ions.
5. The electrode according to claim 1, wherein the cation and anion species are one or more of inorganic cations, inorganic anions, organic cations, organic anions, complex ions and complex ions;
preferably, the inorganic cations include: one or more of hydrogen ions, ammonium ions, potassium ions, sodium ions, calcium ions, magnesium ions, aluminum ions, zinc ions, iron ions, tin ions, lead ions, bismuth ions, mercury ions, silver ions, gold ions, platinum ions, palladium ions, iridium ions, indium ions, titanium ions, vanadium ions, chromium ions, manganese ions, cobalt ions, nickel ions, copper ions, niobium ions, zirconium ions, and hydrated ions of the above ions, and organic complex ions of the above ions, and inorganic complex ions containing the above metal ions;
preferably, the inorganic anions include: one or more of a hydroxide ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a sulfide ion, a silicon ion, a nitrogen ion, a phosphate ion, an arsenic ion, a carbonate ion, a nitrate ion, a hydrate ion of the above ions, an organic complex ion of the above ions, an oxygen acid radical ion containing the above ion element, and a metal complex ion containing the above ion element;
preferably, the organic cations include: one or more of primary amine ions, secondary amine ions, tertiary amine ions, quaternary amine ions, organic phosphorus ions, imidazole cations, pyridine cations, sulfonimide ions, sulfonamide ions, and derived ions thereof;
preferably, the organic anions include: one or more of organic sulfonic acid ions, organic phosphoric acid ions, organic boric acid ions, oxalic acid ions, carbonic acid ions, acetic acid ions, and derived ions of the foregoing ions.
6. The electrode of claim 1, wherein: the electronic conductor is one or more than two of commercialized carbon nano-tube, graphene, carbon nano-fiber, BP2000, KB600, KB300, XC-72, Super-P, acetylene black and active carbon;
the active substance is one or more than two of active carbon, carbon fiber, carbon nano tube, graphite and carbon aerogel.
7. The electrode of claim 1, wherein: the electrolyte can be one or more of liquid electrolyte, solid electrolyte or gel electrolyte; the liquid electrolyte solute is the salt of the anion and the cation, and the solvent is one or more than two of Polycarbonate (PC), Ethylene Carbonate (EC) and diethyl carbonate (DEC); the solid electrolyte is a mixture of the salt of the anions and cations and polyethylene oxide (PEO) polymer or a garnet solid electrolyte; the gel electrolyte solute is the anion and cation salt, and the gel polymer is one or more of polyethylene oxide (PEO), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polymethyl methacrylate (PMMA) and polyvinyl acetal (PVB/PVFM).
8. A method for producing an electrode according to any one of claims 1 to 7, wherein an electrode comprising an electron conductor and an active material, or an electrode comprising an electron conductor, an active material and an electrolyte is first produced as follows: 1) filling electrolyte between the two electrodes, applying an electric field on the two electrodes to transfer electrons between the two electrodes, and in the process, directionally transferring anions and cations in the electrolyte to the two electrodes respectively and achieving balance; 2) controlling the total amount of ions transferred between the two electrodes by controlling the electric field intensity and the electric field time; 3) quickly cutting off an ion transmission channel between the two electrodes to obtain electrodes with different total amounts of anions and cations; after the ion channel is cut off, two electrodes with net electricity are obtained at the same time, and the two electrodes are respectively provided with residual electrons or residual holes; wherein the absolute value of the charge of the anion and the charge of the cation which are carried by each electrode are not equal.
9. Use of an electrode according to any one of claims 1 to 7 in electrochemical energy storage, comprising one of a lithium ion supercapacitor, a sodium ion supercapacitor, and a metal ion battery, wherein the metal ion is one of sodium ion, magnesium ion, potassium ion, calcium ion, or aluminum ion.
10. The use of the electrode of claim 9, said electrochemical energy storage device comprising a positive electrode, a negative electrode, a separator, an electrolyte, and an encapsulating material; wherein the electrolyte is in a solid, liquid or colloidal state;
the application of the electrode in the lithium ion super capacitor comprises the following specific processes: 1) contacting a working electrode containing an activated carbon material with an electrolyte capable of conducting lithium ions, the other side of the electrolyte being in contact with a counter electrode; 2) applying an electric field between the working electrode and the counter electrode: when the electrons are gathered to one side of the working electrode, lithium ions are gathered to one side of the working electrode, and an electric double layer is formed at the interface of the working electrode, wherein the content of the lithium ions in the electric double layer exceeds the total charge carried by anions; 3) the proportion and the content of lithium ions in the double electric layers are regulated and controlled by controlling the time of the action of the electric field; 4) separating the working electrode from the electrolyte body, the working electrode being provided with an electric double layer; 5) the working electrode is used as the positive electrode of the lithium ion super capacitor, and the working electrode, the electrolyte and the new negative electrode form a new hybrid super capacitor, and the active substance of the new negative electrode is one or more than two of lithium titanate, hard carbon, soft carbon, silicon, niobium oxide and graphite;
or, the application of the electrode in the sodium ion super capacitor is as follows: 1) contacting a working electrode containing an activated carbon material with an electrolyte capable of conducting sodium ions, the other side of the electrolyte being in contact with a counter electrode; 2) applying an electric field between the working electrode and the counter electrode: when the electrons are gathered to one side of the working electrode, sodium ions are gathered to one side of the working electrode, and an electric double layer is formed at the interface of the working electrode, wherein the content of the sodium ions in the electric double layer exceeds the total charge carried by anions; 3) the proportion and the content of sodium ions in the double electric layers are regulated and controlled by controlling the time of the action of the electric field; 4) separating the working electrode from the electrolyte body, the working electrode being provided with an electric double layer; 5) the working electrode is used as the positive electrode of the sodium ion super capacitor, and forms a new mixed super capacitor with electrolyte and a new negative electrode, and the active substance of the new negative electrode is one or more than two of sodium titanate, hard carbon, soft carbon, sodium titanium phosphate and graphite;
or, the application of the electrode in the metal ion battery is as follows: 1) contacting a working electrode comprising a metal ion releasable material with an electrolyte capable of conducting metal ions, the other side of the electrolyte being in contact with a counter electrode; 2) applying an electric field between the working electrode and the counter electrode: when the electrons are gathered to one side of the working electrode, metal ions are gathered to one side of the working electrode, and an electric double layer is formed at the interface of the working electrode, wherein the content of the metal ions in the electric double layer exceeds the total charge carried by anions; 3) the proportion and the content of metal ions in the double electric layers are regulated and controlled by controlling the time of the action of the electric field; 4) separating the working electrode from the electrolyte body, wherein the working electrode is provided with an electric double layer with excessive metal ions; 5) the working electrode is used as the positive electrode of the metal ion battery, and forms new metal ions with the electrolyte and the new negative electrode, the active substance of the new negative electrode is one or more than two of hard carbon, soft carbon or graphite, the active substance of the new negative electrode can also be lithium titanate in the case of the lithium ion battery, and the active substance of the new negative electrode can also be sodium titanate and sodium titanium phosphate in the case of the sodium ion battery.
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