WO2015021788A1 - 一种水系碱性电化学储能器件 - Google Patents
一种水系碱性电化学储能器件 Download PDFInfo
- Publication number
- WO2015021788A1 WO2015021788A1 PCT/CN2014/075607 CN2014075607W WO2015021788A1 WO 2015021788 A1 WO2015021788 A1 WO 2015021788A1 CN 2014075607 W CN2014075607 W CN 2014075607W WO 2015021788 A1 WO2015021788 A1 WO 2015021788A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- potassium
- sodium
- lithium
- alkali metal
- storage device
- Prior art date
Links
- 238000012983 electrochemical energy storage Methods 0.000 title claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000011734 sodium Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000007774 positive electrode material Substances 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 239000007773 negative electrode material Substances 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- -1 alkali metal salt Chemical class 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 230000002441 reversible effect Effects 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000003487 electrochemical reaction Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 235000007686 potassium Nutrition 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 13
- 239000010405 anode material Substances 0.000 abstract description 6
- 230000007935 neutral effect Effects 0.000 abstract description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 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 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- VNWKTOKETHGBQD-YPZZEJLDSA-N carbane Chemical class [10CH4] VNWKTOKETHGBQD-YPZZEJLDSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 241000580063 Ipomopsis rubra Species 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- KBAYZRBSZAGGOT-UHFFFAOYSA-N disodium dioxido(oxo)manganese Chemical group [Na+].[Na+].[O-][Mn]([O-])=O KBAYZRBSZAGGOT-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011262 electrochemically active material Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
- H01M10/24—Alkaline accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to the field of new energy materials, and relates to an aqueous alkaline electrochemical energy storage device.
- BACKGROUND OF THE INVENTION With the development of science, technology, economy and society, energy and environmental issues are receiving more and more attention, energy demand continues to skyrocket, and the shortage of fossil energy and environmental damage have turned the focus to renewable resources such as wind and solar energy. However, these renewable energy sources are greatly affected by weather and time periods, and have obvious characteristics of instability, discontinuity and uncontrollability. It is necessary to develop and construct supporting electrical energy storage (storage energy) devices to ensure continuous power generation and power supply. Sex and stability.
- CN1328818C discloses a hybrid water-based lithium ion battery.
- the working principle is: For the assembled battery, it must first be charged. During the charging process, lithium ions are removed from the positive electrode, and lithium ions are adsorbed to the negative electrode made of a material such as activated carbon through the electrolyte. During the discharge process, lithium ions are desorbed from the negative electrode, and lithium ions are inserted into the positive electrode through the electrolyte. The charge and discharge process involves only the transfer of lithium ions between the two electrodes.
- the positive electrode material of the hybrid water-based lithium ion battery is LiMn 2 0 4 , LiCo0 2 , LiCo 1/3 Ni 1/3 Mn 1/3 0 2 , LiMgo.2Mm.sO4 can reversibly intercalate lithium ion-extracting materials, and the negative electrode uses activated carbon, mesoporous carbon or carbon nanotubes having a specific surface area of 1000 m 2 /g or more.
- the demand for lithium will become larger and larger, and the price of lithium materials will become higher and higher due to the limited reserves in the earth's crust.
- Cide-dielectric styrene aqueous phase electrolyte electrochemical secondary energy storage device mainly composed of sodium ions, which comprises an anode electrode, a cathode electrode capable of reversibly deintercalating sodium cations, a separator and a sodium cation.
- an aqueous electrolyte wherein the initial active cathode electrode material comprises an alkali metal-containing active cathode electrode material that deintercalates alkali metal ions during initial charging of the device.
- the active cathode electrode material may be ⁇ - ⁇ 0 2 , NaMn0 2 (sodium manganite structure), Na 2 Mn 3 0 7 , NaFeP0 4 F, Na 0 . 44 MnO 2 .
- the anode electrode comprises porous activated carbon and the electrolyte comprises sodium sulfate.
- Chinese Patent Publication No. CN1723578A discloses a sodium ion battery comprising a positive electrode, a negative electrode and an electrolyte.
- the positive electrode includes an electrochemically active material capable of reversibly circulating sodium ions
- the negative electrode includes a carbon capable of intercalating sodium ions.
- the active material includes a sodium transition metal phosphate.
- the transition metal includes a transition metal selected from the group consisting of vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), nickel (Ni), and titanium (Ti), and mixtures thereof.
- Chinese Patent Publication No. CN101241802A discloses an asymmetric water-based sodium/potassium battery capacitor composed of a positive electrode, a negative electrode, a separator and an electrolyte.
- the active materials of the positive electrode are NaMn0 2 , NaCo0 2 , NaV 3 0 8 , NaVP0 4 F, and Na 2 VOP0 4 .
- the positive electrode active material is uniformly mixed with carbon black and a binder, coated on a nickel mesh current collector, dried and pressed into an electrode.
- the activated carbon is mixed with a conductive agent and a binder, uniformly coated on a nickel mesh current collector, dried and pressed into an electrode.
- a non-woven fabric was used as a separator, and sodium chloride or sodium sulfate was used as an electrolyte to assemble a battery.
- An aqueous alkaline electrochemical energy storage device of the present invention comprises a positive electrode, a negative electrode, a separator and an alkaline electrolyte containing an alkali metal ion, characterized in that the positive electrode material has the general formula A x M n 0 2 The alkali metal-containing manganate, wherein A is selected from one or two of Na and K, 0 ⁇ ⁇ ⁇ 1.
- the present invention relates to an aqueous alkaline electrochemical energy storage device characterized in that the positive electrode material is an alkali metal manganate having the general formula A x Mn0 2 , and A in the A x Mn0 2 is a metal potassium ( When K), the potassium manganate cathode material has a layered crystal structure, and the interplanar spacing of the layered structure is above 7 A, which is larger than the ion diameter of potassium and sodium ions, and after being prepared into an electrode material, The alkali metal ion can be freely removed or embedded, and thus can be used as a positive electrode material having an alkali metal ion deintercalation mechanism in an aqueous alkaline secondary battery.
- the positive electrode material is an alkali metal manganate having the general formula A x Mn0 2
- a in the A x Mn0 2 is a metal potassium
- the potassium manganate cathode material has a layered crystal structure, and the interplanar spacing of the layered structure
- the invention relates to an aqueous alkaline electrochemical energy storage device, characterized in that the electrolyte is an alkaline aqueous solution.
- the alkaline aqueous solution may be an aqueous solution of an alkali metal salt having a pH ⁇ 9, and includes lithium sulfate, lithium nitrate, lithium halide, lithium carbonate, lithium phosphate, lithium acetate, sodium sulfate, sodium nitrate, sodium sulphate, sodium carbonate, sodium phosphate.
- the metal manganate-containing compound can undergo a stable reversible cycle in the alkaline aqueous solution and has a higher specific capacity than in the corresponding neutral aqueous solution.
- the invention relates to an aqueous alkaline electrochemical energy storage device, characterized in that the electrolyte is an alkaline aqueous solution.
- the alkaline aqueous solution may be one or more of lithium hydroxide, sodium hydroxide, and potassium hydroxide.
- the metal manganate-containing compound is stably reversibly circulated in the alkaline aqueous solution at a capacity close to 100 mAh/g.
- the invention relates to an aqueous alkaline electrochemical energy storage device, characterized in that the negative electrode material comprises at least one material capable of reversible electrochemical reaction in an alkaline electrolyte, which may be selected from the group consisting of metal zinc, aluminum, Iron, cadmium, magnesium, lead and their alloys or metal compounds. These metals and their compounds as negative electrode materials cannot be reversibly circulated or even inoperable in a neutral aqueous solution, but reversible dissolution and deposition reactions can be carried out at a relatively high capacity in an alkaline aqueous solution.
- the present invention relates to an aqueous alkaline electrochemical energy storage device, characterized in that the negative electrode material comprises at least one material capable of performing intercalation and extraction of alkali metal ions in an alkaline electrolyte.
- the negative electrode material is selected from one or more porous carbon materials of activated carbon, graphene, carbon nanotubes, carbon fibers and mesoporous carbon.
- An advantage of the present invention is that a plurality of alkaline electrolytes are applied to an aqueous alkaline electrochemical energy storage device that replaces the conventionally used neutral electrolyte, so that the selection of the anode material becomes diversified.
- the invention also features the selection of a novel positive electrode material and the combination of a novel positive electrode material and an alkaline electrolyte in an aqueous alkaline electrochemical energy storage device.
- the invention provides a water-based alkaline electrochemical energy storage device.
- FIG. 1 is a graph showing charge and discharge curves of an asymmetric capacitor-alkali metal ion battery composed of a positive electrode material N a 44 M n 0 2 prepared in Example 1 of the present invention and an activated carbon negative electrode in 6 M NaOH. 2 is an X-ray powder diffraction (XRD) pattern of K Q .
- XRD X-ray powder diffraction
- FIG. 1 is a scanning electron microscope (SEM) image of K Q .
- FIG. 4 is a graph showing charge and discharge curves of an asymmetric capacitor-alkali metal ion battery composed of a layered positive electrode material K a27 Mn0 2 and an activated carbon negative electrode in a saturated LiOH in Example 2 of the present invention.
- Fig. 5 is a graph showing charge and discharge curves of an asymmetric capacitor-alkali metal ion battery composed of a layered positive electrode material K Q .
- Fig. 6 is a graph showing charge and discharge curves of an asymmetric capacitor-alkali metal ion battery composed of a layered positive electrode material K Q . 27 Mn0 2 and an activated carbon negative electrode in 6 M KOH in Example 2 of the present invention.
- Fig. 7 is an asymmetric capacitor composed of a layered positive electrode material ⁇ 27 ⁇ 0 2 and an activated carbon negative electrode in Example 2 of the present invention - an alkali metal ion battery of 1 M Li 2 S0 4 having a pH of 9, 11 and 13 respectively containing LiOH. Charge and discharge curves in aqueous solution.
- Fig. 6 is a graph showing charge and discharge curves of an asymmetric capacitor-alkali metal ion battery composed of a layered positive electrode material K Q . 27 Mn0 2 and an activated carbon negative electrode in 6 M KOH in Example 2 of the present invention.
- Fig. 7 is an asymmetric capacitor composed of a layered positive electrode material ⁇ 27 ⁇ 0 2 and an
- Example 8 is a graph showing charge and discharge curves of a water-based alkaline secondary battery composed of a layered positive electrode material ⁇ 27 ⁇ ⁇ 0 2 and a metal zinc negative electrode in a mixed solution of saturated LiOH and 1 M ZnS 0 4 in Example 3 of the present invention.
- BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the technical solutions of the present invention will be described by using specific embodiments, but the scope of protection of the present invention is not limited thereto:
- Example 1 Sodium carbonate and electrolytic manganese dioxide are mixed in a stoichiometric ratio, uniformly ground, and then Calcination at 900 ° C for 10 h gave Na a44 Mn0 2 .
- the separator was a hydrophilically treated PP-based separator.
- the electrolyte was a 6 M NaOH aqueous solution, and the current intensity was 10 mA/g.
- BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph showing the charge and discharge curves of Na Q . 44 Mn0 2 in different cycles of 6 M NaOH aqueous solution according to an embodiment of the present invention.
- Example 2 Potassium carbonate and electrolytic manganese dioxide were mixed in a stoichiometric ratio, uniformly ground, and then sintered in an air oven at 550 ° C for 8 h, washed three times with water, and dried to prepare a layered ⁇ 27 ⁇ 0 2 .
- X-ray powder diffraction (XRD) pattern of the layered K Q . 27 Mn0 2 synthesized in the examples of the present invention is shown in Fig. 2 .
- Figure 3 is a representation of K in an embodiment of the invention.
- SEM Scanning electron microscopy
- the separator was a hydrophilically treated PP-based separator.
- the electrolytes were saturated LiOH, 6M NaOH, 6M KOH aqueous solution and LiOH-containing pH of 9, respectively. , 11, 13 of 1M Li2S04 aqueous solution, current intensity is 10 mA / g.
- Example 4-7 are charge and discharge curves of an embodiment of the present invention K Q. 27 Mn0 2 in a saturated LiOH aqueous solution, 6 M NaOH, a 6 M aqueous KOH solution, and an alkaline electrolyte of different pH.
- Example 3 The layered K Q . 27 Mn0 2 prepared in Example 2 was used as a positive electrode material.
- the negative electrode material was a 99.99% pure metal zinc plate having a size of 0.5 mm x lcm x lcm (thickness x length x width).
- the positive electrode tab and the negative electrode tab are separated by a hydrophilically treated pp-based separator, and the positive and negative electrodes are pressed with an organic glass plate, and placed in a mixed solution of saturated LiOH and 1M ZnS0 4 for charge and discharge cycle test.
- the current intensity is 200 mA/g, and the charge and discharge curve is shown in Fig. 8.
- metal aluminum, iron, cadmium, magnesium, lead, and alloys thereof or metal compounds thereof can be used as the anode material.
- LiMn 2 0 4 activated carbon saturated LiOH 10 0.2-1.8 116.8 (can not reversible cycle)
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Abstract
本发明涉及水系碱性电化学储能器件。本发明的一种水系碱性储能器件，包括正极、负极、隔膜和含碱金属离子的碱性电解液，其特征在于，该正极材料是具有通式AxMnO2的含碱金属锰酸盐，其中A选自Na和K中的一种或两种， 0<x≤1。碱性电解液打破了在中性电解液中负极材料选择少的限制，使得负极材料的选择变得多元化，可以为大规模储能提供多种低成本、环保安全的技术选择。
Description
一种水系碱性电化学储能器件 技术领域 本发明属于新能源材料技术领域， 涉及一种水系碱性电化学储能器件。 背景技术 随着科技、 经济和社会的发展， 能源和环境问题越来越受到关注， 能源方面需 求持续暴涨，化石能源的短缺和对环境造成的破坏使关注点转向了风能、太阳能这些 可再生资源， 然而这些可再生能源受天气及时间段的影响较大， 具有明显的不稳定、 不连续和不可控等特点， 需要开发和建设配套的电能储存 （储能） 装置来保证发电、 供电的连续性和稳定性。 因此， 大规模储能技术是大力发展太阳能、 风能等可再生能 源利用和智能电网的关键。在所有的储能技术中， 电池可以实现化学能与电能之间的 高效转换， 是一种最佳的能量储存技术。二次可充电池是目前使用最广泛的一种储能 方式。 与其它储能方式相比， 电化学储能能够适应不同的电网功能需要， 在风电、 光 电等的集成并网方面尤其具有优势。对于可充电池储能技术的推广方面来说，存在这 两大挑战。 第一是开发具有高电压和高能量的电池系统， 第二是使用成本低、 稳定、 对环境完全友好、长寿命的电池体系， 以保证源源不断的电能从可再生清洁能源中整 合到电网中。 目前， 用于大型电网储能的方式， 在实际布建的案例中， 还是以传统的铅酸电 池为主。铅酸电池成本低、但是寿命短、铅和浓硫酸等主要材料对环境造成严重污染， 需要回收。 因此， 迫切需要找到一种可以替代铅酸电池的新技术。 近二十年来， 锂离子电池技术的发展日益成熟， 由于其能量密度大， 输出电压 高， 使得锂离子电池在不同领域的应用也得到了迅猛发展。但是由于锂离子电池使用 有机溶剂作为电解液， 由此造成了制造成本偏高以及在使用中有易燃易爆的安全隐 患。中国专利授权公告号 CN1328818C公开了一种混合型水系锂离子电池。其工作原 理是： 对装成的电池， 首先必须进行充电。 充电过程中， 锂离子从正极脱出， 通过电 解液， 锂离子吸附在活性碳等材料做成的负极。 放电过程中， 锂离子从负极上脱附， 通过电解液， 锂离子嵌入正极。充放电过程仅涉及锂离子在两电极间的转移。该混合 型水系锂离子电池的正极材料采用 LiMn204、 LiCo02、 LiCo1/3Ni1/3Mn1/302、
LiMgo.2Mm.sO4等能够可逆的嵌入脱出锂离子的材料， 负极则采用比表面积在 1000m2/g以上的活性炭、 介孔碳或碳纳米管等。 另外， 随着锂离子电池的大规模应用， 锂的需求量会越来越大， 由于地壳中有 限的储量， 导致锂材料的价格会越来越高。近年来人们开始关注用更为廉价的碱金属 如钠， 钾甚至是碱土金属镁来取代锂用于储能器件。钠在地壳中的储量非常丰富， 约 占 2.74 %， 为第六丰富元素， 分布广泛， 含钠的原料价格较低； 以及和锂相似的电化 学性质， 钠基的电池渐渐成为了锂离子电池的替代选择。 早期研究的基于钠金属的钠硫和 Na/NiCl2电池，虽然具有较为理想的能量密度， 但是要用到熔融态的钠作为负极， 运行温度在 300〜350°C之间， 因此需要配套使用 高额的热管理体系和特殊的陶瓷固体电解质。另外如果陶瓷固体电解质一旦破损形成 短路， 高温的液态钠和硫就会直接接触， 发生剧烈的放热反应， 产生 2000°C的高温， 有较大的安全隐患。 基于这些背景和原因， 室温钠离子电池又成为人们的研究热点。 中国专利公开号 CN102027625A公开了一种以钠离子为主的水相电解质电化学 二次能源储存装置， 其包括阳极电极、 能够使钠阳离子可逆性脱嵌的阴极电极、 隔板 和含有钠阳离子的水相电解质，其中初始活性阴极电极材料包含在该装置的初始充电 期间使碱金属离子脱嵌的含碱金属的活性阴极电极材料。该活性阴极电极材料可以是 惨铝的 λ-Μη02、 NaMn02(水钠锰矿结构）、 Na2Mn307、 NaFeP04F、 Na0.44MnO2。 该 阳极电极包含多孔活性炭， 且电解质包含硫酸钠。 中国专利公开号 CN1723578A公开了一种钠离子电池， 包括正电极、 负电极和 电解质。正电极包括一种能够可逆性循环钠离子的电化学活性材料， 负电极包括一种 能够嵌入钠离子的碳。该活性材料包括钠过渡金属磷酸盐。过渡金属包括选自钒（ V)、 锰 （Mn)、 铁 （Fe)、 钴 （Co)、 铜 （Cu)、 镍 （Ni)、 钛 （Ti) 中的一种过渡金属及其 混合物。 中国专利公开号 CN101241802A 公开了一种非对称型水系钠 /钾离子电池电容 器，由正极、负极、隔膜和电解质组成。正极的活性材料为 NaMn02、NaCo02、NaV308、 NaVP04F和 Na2VOP04。将正极活性材料与炭黑、粘结剂混合均匀， 涂布在镍网集流 体上，烘干后压成电极。将活性炭与导电剂和粘结剂混合，均匀涂布在镍网集流体上， 烘干后压成电极。采用无纺布作为隔膜，用氯化钠或硫酸钠作为电解液，组装成电池。
但是， 以上被研究的含碱金属盐的正极材料，在含钠 /钾离子的水溶液中使用时， 只能用活性炭这一类多孔碳材料作为负极组成非对称电容器 -碱金属离子电池， 并且 只有在偏中性的水溶液中才能可逆循环。 多孔碳材料的比容量低， 成本高， 负极材料 的选择成了水系二次电池应用的一个技术瓶颈。因此期望一种新型的水系碱性电化学 储能器件， 其中可以多元化地选择负极材料。 发明内容 本发明的一种水系碱性电化学储能器件， 包括正极、 负极、 隔膜和含碱金属离 子的碱性电解液， 其特征在于， 该正极材料是具有通式AxMn02的含碱金属锰酸盐， 其中 A选自 Na和 K中的一种或两种， 0<χ≤1。 本发明涉及的一种水系碱性电化学储能器件， 其特征在于， 该正极材料是具有 通式 AxMn02的含碱金属锰酸盐， 当 AxMn02中的 A是金属钾 （K) 时， 该锰酸钾正 极材料具有层状晶体结构， 这种层状结构的晶面间距在 7 A 以上， 比钾和钠离子的 离子直径还大， 在制备成电极材料以后，， 使得碱金属离子能够自由进行脱出或者嵌 入， 因此可作为具有碱金属离子脱嵌机制的正极材料在水系碱性二次电池中应用。 本发明涉及的一种水系碱性电化学储能器件， 其特征在于其电解液是碱性水溶 液。该碱性水溶液可以是 pH≥9的碱金属盐的水溶液， 包含硫酸锂、硝酸锂、 卤化锂、 碳酸锂、 磷酸锂、 醋酸锂、 硫酸钠、 硝酸钠、 ¾化钠、 碳酸钠、 磷酸钠、 醋酸钠、 高 氯酸钠、 硫酸钾、 硝酸钾、 ¾化钾、 碳酸钾、 磷酸钾、 醋酸钾、 高氯酸钾中的一种或 多种。含金属锰酸盐在该碱性水溶液中可以进行稳定的可逆循环， 并且比在相应的中 性水溶液中比容量高。 本发明涉及的一种水系碱性电化学储能器件， 其特征在于其电解液是碱性水溶 液。 该碱性水溶液可以是含氢氧化锂、 氢氧化钠、 氢氧化钾中的一种或多种。 含金属 锰酸盐在所述碱性水溶液中以接近 lOOmAh/g的容量稳定可逆循环。 本发明涉及的一种水系碱性电化学储能器件， 其特征在于， 所述负极材料至少 包含一种能够在碱性电解液中进行可逆电化学反应的材料，可以选自金属锌、铝、铁、 镉、镁、 铅及其合金或金属化合物。这些作为负极材料的金属及其化合物在中性水溶 液中不能可逆循环，甚至是不能工作的，但是在碱性的水溶液中便能以较高的容量进 行可逆的溶解和沉积反应。
本发明涉及的一种水系碱性电化学储能器件， 其特征在于， 所述负极材料至少 包含一种能够在碱性电解液中进行碱金属离子的嵌入和脱出的材料。当碱金属离子在 正极和负极之间进行嵌入脱出循环时， 形成一种水系的"摇椅"电池。 本发明涉及的一种水系碱性电化学储能器件， 其特征在于， 所述负极材料选自 活性炭、 石墨烯、 碳纳米管、 碳纤维和介孔碳中的一种或多种多孔碳材料。 这些材料 均是靠大的表面积进行非法拉第双电层电子吸附过程， 与正极组成混合电容电池。 本发明的优点在于将多种碱性电解液应用于水系碱性电化学储能器件， 该碱性 电解液替代了传统上使用的中性电解液， 使得负极材料的选择变得多元化。 本发明的特点还在于新型正极材料的选择以及新型正极材料与碱性电解液的组 合在水系碱性电化学储能器件中的应用。 本发明提供了一种水系碱性电化学储能器件， 碱性电解液打破了在中性电解液 中负极材料选择少的限制， 使得负极材料的选择变得多元化，水系电化学电池的发展 提供了一种新的产业化方案， 可以为大规模储能提供多种低成本、环保安全的技术选 择。 附图说明 图 1是本发明实施例 1 中制备的正极材料 Na 44Mn02与活性炭负极组成的非 对称电容器 -碱金属离子电池在 6M NaOH中的充放电曲线。 图 2 是本发明实施例 2 中制备的层状材料的 KQ.27Mn02 的 X 射线粉末衍射 (XRD) 图 （Cu Ka = 0.15406 nm)。 图 3 是本发明实施例 2 中制备的层状材料的 KQ.27Mn02 的扫描电镜 （SEM) 图。 图 4 是本发明实施例 2 中层状正极材料材料 Ka27Mn02 与活性炭负极组成的 非对称电容器-碱金属离子电池在饱和 LiOH中的充放电曲线。 图 5是本发明实施例 2中层状正极材料材料 KQ.27Mn02 与活性炭负极组成的非 对称电容器 -碱金属离子电池在 6M NaOH中的充放电曲线。
图 6是本发明实施例 2 中层状正极材料材料 KQ.27Mn02 与活性炭负极组成的 非对称电容器 -碱金属离子电池在 6M KOH中的充放电曲线。 图 7 是本发明实施例 2 中的层状正极材料材料 Κ 27Μη02 与活性炭负极组成 的非对称电容器-碱金属离子电池在含有 LiOH的 pH分别为 9， 11 , 13的 1M Li2S04 水溶液中的充放电曲线。 图 8 是本发明实施例 3中的层状正极材料材料 Κ 27Μη02 与金属锌负极组成的 水系碱性二次电池在饱和 LiOH与 1M ZnS04的混合溶液中的充放电曲线。 具体实施方式 以下用具体实施例来说明本发明的技术方案， 但是本发明的保护范围并不局限 于此： 实施例 1 将碳酸钠和电解二氧化锰按化学计量比混合， 研磨均匀， 然后在 900°C煅烧 10h 得到 Naa44Mn02。 正极材料按照 Na0.44MnO2 : 乙炔黑： PTFE粘结齐 U = 80: 10: 10的质 量比均匀混合， 烘干后将混合物辊压或碾压到不锈钢网上， 然后制成 0.2mm厚的电 极片。负极材料采用商业化的活性炭，按照活性炭：导电炭黑： PTFE粘结剂 = 80: 10: 10 的质量比均匀混合， 烘干后将混合物辊压或碾压到不锈钢网上， 然后制成 0.8 mm厚 的电极片。 然后将正负极电极按照规格裁切， 配对组装成 CR2032纽扣电池， 隔膜采 用亲水处理过的 PP基隔膜， 电解液是 6M NaOH水溶液， 电流强度是 10mA/g。 图 1 是本发明实施例 NaQ.44Mn02在 6M NaOH水溶液中不同循环的的充放电曲线。 实施例 2 将碳酸钾和电解二氧化锰按化学计量比混合， 研磨均匀， 然后在空气炉 550 °C 中烧结 8 h， 水洗三次， 干燥处理， 即制备得到层状的 Κ 27Μη02。 本发明实施例中 合成的层状 KQ.27Mn02 的 X射线粉末衍射 （XRD ) 图参见图 2。 图 3是本发明实施 例中 K。.27Mn02的扫描电镜（SEM) 图。 正极材料按照 K。.27Mn02 : 乙炔黑： PTFE粘 结剂 = 85:7:8 的质量比均匀混合， 烘干后将混合物辊压或碾压到不锈钢网上， 然后 制成 0.2mm厚的电极片。 负极材料采用商业化的活性炭， 按照活性炭： 导电炭黑： PTFE 粘结剂 = 85:7:8 的质量比均匀混合， 烘干后将混合物辊压或碾压到不锈钢网
上， 然后制成 0.8 mm 厚的电极片。 然后将正负极电极按照规格裁切， 配对组装成 CR2032纽扣电池， 隔膜采用亲水处理过的 PP基隔膜， 电解液分别是饱和 LiOH、 6M NaOH、6M KOH水溶液和含有 LiOH的 pH分别为 9， 11, 13的 1M Li2S04水溶液， 电 流强度是 10 mA/g。 图 4-7分别是本发明实施例 KQ.27Mn02在饱和 LiOH水溶液、 6M NaOH、 6M KOH水溶液和不同 pH的碱性电解液中的充放电曲线。 实施例 3 采用实施例 2中制备的层状 KQ.27Mn02作为正极材料。正极材料按照 KQ.27Mn02 : 乙炔黑： PTFE粘结剂 = 80:10:10的质量比均匀混合， 烘干后将混合物辊压或碾压到 不锈钢网上， 然后制成 0.2mm厚的电极片。 负极材料采用 99.99%纯度的金属锌片， 尺寸为 0.5mmx lcmx lcm (厚 x长 x宽）。 将正极极片与负极极片中间用亲水处理过的 pp基隔膜隔开， 并且用有机玻璃板将正负极压紧， 置于饱和 LiOH与 1M ZnS04的混 合溶液中进行充放电循环测试， 电流强度为 200 mA/g， 充放电曲线如图 8所示。 作 为该实施例的变型例， 可以使用金属铝、 铁、 镉、 镁、 铅及其合金或金属化合物作为 负极材料。 以下的表 1是不同的含金属锰酸盐AxMn02 (A = Na、 K) 作为正极材料， 与不 同的负极进行组合， 在不同的碱性水溶液中进行可逆循环的放电比容量以及第 10个 循环后的容量保持率。 表 1 电压 放电 第 10个循 负极
正极材料 电解液 范围 比容量 环的容量 材料
(V) (mAh/g) 保持率
Na0.44MnO2 活性炭 6M NaOH 10 0.2-1.5 92.4 100%
Na0.44MnO2 活性炭 lM Na2S04 10 0.2-1.5 42.3 92%
Ko.2vMn02 活性炭 饱和 LiOH 10 0.2-1.6 113.8 97%
Ko.2vMn02 活性炭 6M NaOH 10 0.2-1.5 101.3 100%
Ko.2vMn02 活性炭 6M KOH 10 0.2-1.4 78.7 94%
Li2S04
Ko.2vMn02 活性炭 10 0.2-1.6 57.4 102%
(pH = 9)
Li2S04
Ko.2vMn02 活性炭 10 0.2-1.6 58.9 92%
(pH = ll)
Li2S04
Ko.2vMn02 活性炭 10 0.2-1.6 61.3 96%
(pH = 13)
饱和 LiOH
Ko.2vMn02 金属锌 /1 M ZnS04 200 0.2-1.7 93.6 84% 混合溶液
ZnS04+
Ko.2vMn02 金属锌 L12SO4 200 0.2-1.7
(不工作）
(pH < 6 )
LiMn204 活性炭 饱和 LiOH 10 0.2-1.8 116.8 (不能可 逆循环）
虽然已经以具体实施例的方式描述了本发明， 但是对于本领域技术人员来说明 显的是，在不脱离所附权利要求书所限定的本发明的精神和范围的情况下， 可以对本 发明进行各种变化和修改， 这些变化和修改同样包括在本发明的范围内。
Claims
1. 一种水系碱性电化学储能器件， 包括正极、 负极、 隔膜和含碱金属离子 的碱性电解液， 其特征在于， 该正极的活性材料是具有通式AxMn02的含碱金属 锰酸盐， 其中 A选自 Na和 K中的一种或两种， 0<χ≤1。
2. 根据权利要求 1 所述的水系碱性电化学储能器件， 其特征在于， 所述的 正极材料为具有通式 AxMn02的含碱金属锰酸盐，其中所述的碱金属 A为钾（K), 并且所述含钾的锰酸盐具有层状晶体结构。
3. 根据权利要求 1 所述的水系碱性电化学储能器件， 其特征在于， 所述的 含碱金属离子的碱性电解液， 为 pH≥9的碱金属盐的水溶液， 包含选自硫酸锂、 硝酸锂、 ¾化锂、 碳酸锂、 磷酸锂、 醋酸锂、 硫酸钠、 硝酸钠、 ¾化钠、 碳酸钠、 磷酸钠、 醋酸钠、 高氯酸钠、 硫酸钾、 硝酸钾、 ¾化钾、 碳酸钾、 磷酸钾、 醋酸 钾、 高氯酸钾中的一种或多种。
4. 根据权利要求 1 所述的水系碱性电化学储能器件， 其特征在于， 所述的 含碱金属离子的碱性电解液， 为 pH≥ll 的碱金属盐的水溶液， 包含硫酸锂、 硝 酸锂、 ¾化锂、 碳酸锂、 磷酸锂、 醋酸锂、 硫酸钠、 硝酸钠、 ¾化钠、 碳酸钠、 磷酸钠、 醋酸钠、 高氯酸钠、 硫酸钾、 硝酸钾、 ¾化钾、 碳酸钾、 磷酸钾、 醋酸 钾、 高氯酸钾中的一种或多种。
5. 根据权利要求 1 所述的水系碱性电化学储能器件， 其特征在于， 所述的 含碱金属离子的碱性电解液， 包含氢氧化锂、 氢氧化钠、 氢氧化钾中的一种或多 种。
6. 根据权利要求 1 所述的水系碱性电化学储能器件， 其特征在于， 所述负 极材料至少包含一种能够在碱性电解液中进行可逆电化学反应的材料，其选自金 属锌、 铝、 铁、 镉、 镁、 铅及其合金或金属化合物。
7. 根据权利要求 1 所述的水系碱性电化学储能器件， 其特征在于， 所述负 极材料至少包含一种能够在碱性电解液中进行碱金属离子的嵌入和脱出的材料。
8. 根据权利要求 1 所述的水系碱性电化学器件， 其特征在于， 所述负极材 料的活性材料选自活性炭、 石墨烯、 碳纳米管、 碳纤维和介孔碳中的一种或多种 材料。
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