CN114039107A - Manganese-zinc secondary battery of oil-water heterogeneous electrolyte system - Google Patents
Manganese-zinc secondary battery of oil-water heterogeneous electrolyte system Download PDFInfo
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- CN114039107A CN114039107A CN202111183719.XA CN202111183719A CN114039107A CN 114039107 A CN114039107 A CN 114039107A CN 202111183719 A CN202111183719 A CN 202111183719A CN 114039107 A CN114039107 A CN 114039107A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 239000011572 manganese Substances 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000011149 active material Substances 0.000 claims abstract description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 33
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 13
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 13
- 229960001763 zinc sulfate Drugs 0.000 claims description 13
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 13
- 229910001437 manganese ion Inorganic materials 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- -1 zinc tetrafluoroborate Chemical compound 0.000 claims description 11
- 229940099596 manganese sulfate Drugs 0.000 claims description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims description 10
- 239000011702 manganese sulphate Substances 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- YISPIDBWTUCKKH-UHFFFAOYSA-L zinc;4-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 YISPIDBWTUCKKH-UHFFFAOYSA-L 0.000 claims description 7
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 7
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 6
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 6
- ZMCVIGZGZXZJKM-UHFFFAOYSA-L zinc;benzenesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 ZMCVIGZGZXZJKM-UHFFFAOYSA-L 0.000 claims description 6
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003014 ion exchange membrane Substances 0.000 claims description 4
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了油‑水异质电解液体系的锰锌二次电池。该锰锌二次电池包括：正极、负极、正极腔室、负极腔室、隔膜、正极电解液和负极电解液，其中，所述正极包括锰基活性物质；所述负极包括金属锌和/或含锌化合物；所述隔膜设在所述正极腔室和所述负极腔室之间并将所述正极腔室和所述负极腔室隔开；所述正极电解液为水系电解液，所述正极电解液位于所述正极腔室内并与所述正极接触；所述负极电解液为油系电解液，所述负极电解液位于所述负极腔室内并与所述负极接触。该锰锌二次电池能够综合利用锌金属电极在油系电解液的优势和锰基正极在水系电解液中的优势，具有电池体系稳定、循环寿命长和安全性高的优点。
The invention discloses a manganese-zinc secondary battery of an oil-water heterogeneous electrolyte system. The manganese-zinc secondary battery includes: a positive electrode, a negative electrode, a positive electrode chamber, a negative electrode chamber, a separator, a positive electrode electrolyte and a negative electrode electrolyte, wherein the positive electrode includes a manganese-based active material; the negative electrode includes metal zinc and/or Zinc-containing compound; the separator is arranged between the positive electrode chamber and the negative electrode chamber and separates the positive electrode chamber and the negative electrode chamber; the positive electrode electrolyte is an aqueous electrolyte, and the The positive electrode electrolyte is located in the positive electrode chamber and is in contact with the positive electrode; the negative electrode electrolyte is an oil-based electrolyte, and the negative electrode electrolyte is located in the negative electrode chamber and is in contact with the negative electrode. The manganese-zinc secondary battery can comprehensively utilize the advantages of zinc metal electrodes in oil-based electrolytes and manganese-based positive electrodes in aqueous electrolytes, and has the advantages of stable battery system, long cycle life and high safety.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a manganese-zinc secondary battery of an oil-water heterogeneous electrolyte system.
Background
Manganese-based (e.g. LiMn)2O4、MnO2) In the case of a battery having zinc as a negative electrode, an aqueous electrolyte solution containing H is often used2O is used as a solvent, and a metal salt electrolyte is added. The water-based electrolyte has no toxicity or harmNon-flammable, low cost and low requirement on production environment. However, in an aqueous solution system, the negative electrode has severe corrosion and hydrogen evolution reaction, which reduces the stability of the battery.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a manganese-zinc secondary battery of an oil-water heterogeneous electrolyte system, which can comprehensively utilize the advantages of a zinc metal electrode in an oil-based electrolyte and the advantages of a manganese-based positive electrode in an aqueous electrolyte, and has the advantages of a stable battery system, a long cycle life and high safety.
The invention is mainly based on the following problems:
the battery using manganese-based zinc as the negative electrode, the negative electrode adopts aqueous electrolyte and has the following defects: 1. the self-corrosion phenomenon of the cathode is very obvious; 2. side reactions are more, and a gas evolution phenomenon exists, so that a battery system is unstable; 2. the self-discharge phenomenon caused by the side reaction of the cathode is serious. The cathode adopts organic electrolyte and has the defects of insufficient gram capacity and insufficient cycling stability of cathode materials.
To this end, in one aspect of the invention, the invention provides a manganese-zinc secondary battery with an oil-water heterogeneous electrolyte system. According to an embodiment of the present invention, the manganese-zinc secondary battery includes:
a positive electrode including a manganese-based active material;
a negative electrode comprising metallic zinc and/or a zinc-containing compound;
a positive electrode chamber and a negative electrode chamber;
a separator disposed between and separating the positive electrode chamber and the negative electrode chamber;
the positive electrode electrolyte is an aqueous electrolyte, and is positioned in the positive electrode cavity and is in contact with the positive electrode;
and the negative electrode electrolyte is an oil-based electrolyte, and is positioned in the negative electrode cavity and is in contact with the negative electrode.
According to the manganese-zinc secondary battery of the oil-water heterogeneous electrolyte system in the embodiment of the invention, the diaphragm is adopted to separate the positive electrode chamber from the negative electrode chamber, so that the liquid phase circulation of the positive electrode electrolysis and the negative electrode electrolyte can be effectively avoided, and the diaphragm can allow electric charges to pass through, therefore, various defects existing when the negative electrode is contacted with the water system electrolyte can be avoided, the problems of serious self-corrosion of the negative electrode, multiple side reactions, hydrogen evolution, self-discharge and the like can be solved, the problems of insufficient gram capacity and poor circulation stability of a positive electrode material existing when the positive electrode is contacted with the organic electrolyte can be avoided, the advantages of a zinc metal electrode in the oil system electrolyte and the advantages of a manganese-based positive electrode in the water system electrolyte can be comprehensively utilized, the hydrogen evolution reaction between the zinc negative electrode and water and the self-corrosion phenomenon of the zinc negative electrode can be blocked, and the growth of dendrites can be further inhibited by the oil system electrolyte, therefore, the manganese-zinc secondary battery has the advantages of stable battery system, long cycle life and high safety.
In addition, the manganese-zinc secondary battery of the oil-water heterogeneous electrolyte system according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the membrane is an ion exchange membrane or a dialysis membrane.
In some embodiments of the present invention, the positive electrode electrolyte includes water, a salt containing a zinc ion, and a salt containing a manganese ion, and the total concentration of cations in the positive electrode electrolyte is not less than 0.1 mol/L.
In some embodiments of the present invention, the salt containing a zinc ion comprises at least one selected from the group consisting of zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctanoate, and the salt containing a manganese ion comprises at least one selected from the group consisting of manganese chloride, manganese sulfate, and manganese nitrate.
In some embodiments of the present invention, the positive electrode electrolyte further includes at least one selected from the group consisting of sodium ions, potassium ions, lithium ions, and magnesium ions.
In some embodiments of the invention, the salt containing zinc ions is zinc sulfate and the salt containing manganese ions is manganese sulfate.
In some embodiments of the present invention, the total concentration of cations in the positive electrode electrolyte is 1 to 2.5 mol/L.
In some embodiments of the present invention, the negative electrode electrolyte includes an organic solvent and a salt containing zinc ions, and a concentration of the zinc ions in the negative electrode electrolyte is not less than 0.1 mol/L.
In some embodiments of the invention, the organic solvent comprises at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and diglyme.
In some embodiments of the invention, the organic solvent further comprises at least one selected from the group consisting of dimethyl carbonate, ethylene carbonate, propylene carbonate, trimethyl phosphate, and triethyl phosphate.
In some embodiments of the invention, the salt comprising a zinc ion comprises at least one selected from the group consisting of zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctoate.
In some embodiments of the invention, the organic solvent is trimethyl phosphate and the salt comprising a zinc ion is zinc tetrafluoroborate.
In some embodiments of the present invention, the concentration of the zinc ion is 1 to 2.5 mol/L.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural view of a manganese-zinc secondary battery of an oil-water heterogeneous electrolyte system according to one embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, the invention provides a manganese-zinc secondary battery with an oil-water heterogeneous electrolyte system. According to an embodiment of the present invention, as shown with reference to fig. 1, the manganese-zinc secondary battery includes: the cathode comprises a cathode 1, a cathode 2, a cathode chamber 3, a cathode chamber 4, a diaphragm 5, a cathode electrolyte 6 and a cathode electrolyte 7, wherein the cathode 1 comprises manganese-based active substances; the negative electrode 2 comprises metallic zinc and/or a zinc-containing compound; the diaphragm 5 is arranged between the positive electrode chamber 3 and the negative electrode chamber 4 and separates the positive electrode chamber 3 from the negative electrode chamber 4; the positive electrolyte 6 is an aqueous electrolyte, and the positive electrolyte 6 is positioned in the positive chamber 3 and is in contact with the positive electrode 1; the negative electrolyte 6 is an oil-based electrolyte, and the negative electrolyte 7 is located in the negative chamber 4 and contacts the negative electrode 2. Compared with the prior art, the manganese-zinc secondary battery has the advantages of stable battery system, long cycle life and high safety.
The manganese-zinc secondary battery of the oil-water heterogeneous electrolyte system according to the above embodiment of the present invention will be described in detail with reference to fig. 1.
According to some embodiments of the present invention, the diaphragm 5 may be an ion exchange membrane or a dialysis membrane, and in order to achieve effective separation of the positive electrolyte and the negative electrolyte, it is desirable to make the diaphragm have a good separation effect, so as to avoid liquid phase circulation of the aqueous electrolyte and the oil electrolyte and further various side reactions, and at the same time, to ensure that the diaphragm can smoothly pass charges (such as charged ions or free electrons), so as to ensure the conductive effect of the battery.
According to some further embodiments of the present invention, the positive electrolyte may include water, a salt containing zinc ions, and a salt containing manganese ions, the total concentration of cations in the positive electrolyte may be not less than 0.1mol/L, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, etc., the positive electrolyte uses water as a solvent, which is not only safe, non-toxic and low in cost, but also has good solubility to salts, can significantly improve the conductivity of the positive electrolyte, and is beneficial to the exertion of battery capacity, thereby effectively solving the problems of insufficient gram capacity and poor cycling stability of the positive electrode material when an organic electrolyte is used; furthermore, zinc ions are used as first ions in the positive electrode electrolyte, and manganese ions are mainly used for inhibiting the dissolution of positive electrode materials such as manganese dioxide, wherein the ratio of the zinc ions to the manganese ions is not particularly limited, and can be selected by a person skilled in the art according to actual needs; in addition, at least one selected from the group consisting of sodium ions, potassium ions, lithium ions, and magnesium ions may be further included as the second ions in the positive electrode electrolyte. In addition, the inventor also finds that the increase of the ion concentration in the electrolyte can reduce the internal resistance of the battery, thereby being more beneficial to the exertion of the battery capacity, and the problem that the battery capacity is influenced due to the overlarge internal resistance of the battery can be avoided by controlling the total concentration of the cations in the positive electrolyte to be not less than 0.1 mol/L; preferably, the total concentration of cations in the positive electrode electrolyte may preferably be 1 to 2.5mol/L, for example, 2mol/L, whereby the exertion of the battery capacity may be further facilitated.
According to further embodiments of the present invention, the kind of the salt containing a zinc ion and the salt containing a manganese ion in the positive electrode electrolyte is not particularly limited and may be selected by those skilled in the art according to actual needs, for example, the salt containing a zinc ion may include at least one selected from the group consisting of zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate, and zinc isooctanoate, and the salt containing a manganese ion may include at least one selected from the group consisting of manganese chloride, manganese sulfate, and manganese nitrate. Preferably, the salt containing zinc ions can be zinc sulfate, and the salt containing manganese ions can be manganese sulfate, so that the zinc sulfate and the manganese sulfate are low in cost and more stable in electrochemical window compared with other zinc salts and magnesium salts, and the comprehensive performance of the battery is better exerted.
According to still other embodiments of the present invention, the negative electrode electrolyte may include an organic solvent and a salt containing zinc ions, wherein the negative electrode electrolyte adopts an organic system, which can improve the stability of the zinc negative electrode, not only prevent the self-corrosion of zinc and water interaction and the adverse effect of hydrogen evolution on the battery, but also facilitate the prevention of the growth of dendrites, and effectively exert the advantages of the negative electrode itself. Furthermore, the concentration of zinc ions in the negative electrode electrolyte can be not less than 0.1mol/L, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L and the like, and the inventor finds that the increase of the ion concentration in the electrolyte can reduce the internal resistance of the battery, thereby being more beneficial to the exertion of the battery capacity, and the problem that the exertion of the battery capacity is influenced due to the overlarge internal resistance of the battery can be further avoided by controlling the total concentration of cations in the negative electrode electrolyte to be not less than 0.1 mol/L; preferably, the total concentration of the cations in the negative electrode electrolyte may be preferably 1 to 2.5mol/L, for example, 2mol/L, thereby further contributing to the exertion of the battery capacity.
According to still further embodiments of the present invention, the kinds of the organic solvent and the salt containing zinc ions in the negative electrode electrolyte are not particularly limited and may be selected by those skilled in the art according to actual needs, for example, the organic solvent may include only at least one selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and diglyme, or may further include at least one selected from the group consisting of dimethyl carbonate, ethylene carbonate, propylene carbonate, trimethyl phosphate, and triethyl phosphate; the zinc ion-containing salt can comprise at least one selected from zinc chloride, zinc tetrafluoroborate, zinc perchlorate, zinc trifluoromethanesulfonate, zinc sulfate, zinc nitrate, zinc oxalate, zinc benzenesulfonate, zinc p-toluenesulfonate and zinc isooctoate.
According to still other embodiments of the present invention, the organic solvent in the negative electrode electrolyte may preferably be trimethyl phosphate, and the salt containing zinc ions may preferably be zinc tetrafluoroborate, and the inventors have found that trimethyl phosphate is environmentally friendly, stable, safe, and non-flammable compared to other organic solvents, and that the use of trimethyl phosphate in combination with zinc tetrafluoroborate can further improve the performance of the electrical properties of the manganese zinc secondary battery compared to other salts containing zinc ions.
In summary, according to the manganese-zinc secondary battery of the oil-water heterogeneous electrolyte system of the above embodiment of the present invention, the separator is used to separate the positive electrode chamber from the negative electrode chamber, so as to effectively avoid the liquid phase circulation between the positive electrode electrolysis and the negative electrode electrolyte, and allow the electric charges to pass through, thereby avoiding various defects existing when the negative electrode contacts with the aqueous electrolyte, solving the problems of serious self-corrosion of the negative electrode, multiple side reactions, hydrogen evolution and self-discharge, etc., and avoiding the problems of insufficient gram volume and poor cycle stability of the positive electrode material existing when the positive electrode contacts with the organic electrolyte, and making comprehensive use of the advantages of the zinc metal electrode in the oil electrolyte and the advantages of the manganese-based positive electrode in the aqueous electrolyte, thereby not only blocking the hydrogen evolution reaction between the zinc negative electrode and water and the self-corrosion phenomenon of the zinc negative electrode, but also further inhibiting the growth of dendrites by using the oil electrolyte, therefore, the advantages of the metal zinc cathode and the manganese-based cathode can be fully exerted, and the adverse effect on the battery caused by the interaction of water molecules and zinc is avoided, so that the manganese-zinc secondary battery has the advantages of stable battery system, long cycle life and high safety.
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Assembling the battery: in MnO2As positive electrode, zinc as negative electrode, and the diaphragm is cation exchange membrane. Anode electrolyte: dissolving water as solvent, zinc sulfate as zinc salt and manganese sulfate as manganese salt in water, Zn2+Mn concentration of 1.2mol/L2+The concentration is 0.2 mol/L; and (3) cathode electrolyte: trimethyl phosphate (TMP) as solvent, zinc tetrafluoroborate as solute, Zn2+The concentration is 1.0 mol/L;
and (3) testing the battery: in an environment of 25 ℃, the battery is firstly discharged under the current density of 125mA/g and the voltage range of 0.8-1.9V, after 5 circles of activation, the initial specific capacity is 130.2mAh/g, the capacity is kept to be 103.4mAh/g after 500 circles of activation, and the capacity retention rate is 79.4%.
Example 2
Assembling the battery: MnO was used in this experiment2As positive electrode, zinc as negative electrode, and the diaphragm is cation exchange membrane. Anode electrolyte: dissolving water as solvent, zinc sulfate as zinc salt and manganese sulfate as manganese salt in water, Zn2+Mn at a concentration of 1.8mol/L2+The concentration is 0.2 mol/L; and (3) cathode electrolyte: trimethyl phosphate (TMP) as solvent, zinc p-toluenesulfonate as solute, Zn2+The concentration is 1.5 mol/L;
and (3) testing the battery: in an environment of 25 ℃, the battery discharges firstly under the current density of 125mA/g and the voltage range of 0.8-1.9V. After 5 cycles of activation, the initial specific capacity is 150.2mAh/g, and the discharge specific capacity is exerted highly; after 500 cycles, the capacity was maintained at 127.1mAh/g, and the capacity retention rate was 84.6%.
Example 3
Assembling the battery: MnO was used in this experiment2As the anode, the metal zinc as the cathode and the diaphragm as the dialysis membrane. Anode electrolyte: dissolving water as solvent, zinc sulfate as zinc salt and manganese sulfate as manganese salt in water, Zn2+Concentration 1.0mol/L, Mn2+The concentration is 0.1 mol/L; and (3) cathode electrolyte: dimethyl sulfoxide as solvent, zinc perchlorate as solute, Zn2+The concentration is 1.0 mol/L;
and (3) testing the battery: in an environment of 25 ℃, discharging the battery at a current density of 125mA/g and a voltage range of 0.8-1.9V, and after 5 circles of activation, the initial specific capacity is 127.7 mAh/g; after 500 cycles, the capacity was maintained at 89.9mAh/g, and the capacity retention rate was 70.4%.
The comprehensive examples 1 to 3 show that the improvement of the ion concentration of the electrolyte is more favorable for the improvement of the discharge specific capacity of the battery, because the ion concentration in the electrolyte is higher, the internal resistance of the battery is lower, and the exertion of the capacity of the battery is more favorable; compare in the dialysis membrane, adopt ion exchange membrane more to be favorable to promoting the circulation stability of battery as the diaphragm, this is because the separation effect of dialysis membrane to water is relatively poor, can introduce certain steam easily when the ion in the positive electrode electrolyte migrates in to the negative electrode electrolyte, along with the increase of cycle number, has destroyed the interface environment of negative electrode liquid, leads to the battery cyclicity variation.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
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