CN109686925A - A kind of Zinc ion battery and its MnO2The preparation method of/C positive electrode material - Google Patents
A kind of Zinc ion battery and its MnO2The preparation method of/C positive electrode material Download PDFInfo
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- CN109686925A CN109686925A CN201710977277.3A CN201710977277A CN109686925A CN 109686925 A CN109686925 A CN 109686925A CN 201710977277 A CN201710977277 A CN 201710977277A CN 109686925 A CN109686925 A CN 109686925A
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- ion battery
- zinc
- positive electrode
- electrode material
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 19
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 150000002696 manganese Chemical class 0.000 claims abstract description 18
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 claims abstract description 12
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 10
- 239000011029 spinel Substances 0.000 claims abstract description 10
- 238000000975 co-precipitation Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 6
- 229910018605 Ni—Zn Inorganic materials 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011656 manganese carbonate Substances 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
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 claims 1
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- AEQYSJQDOAMFHE-UHFFFAOYSA-N [Zn].FCS(=O)(=O)O Chemical compound [Zn].FCS(=O)(=O)O AEQYSJQDOAMFHE-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910019426 CoxO4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PRPFRZNWBZVUPC-UHFFFAOYSA-N [Mn].[Zn].[Li] Chemical compound [Mn].[Zn].[Li] PRPFRZNWBZVUPC-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to Zinc ion battery field, a kind of Zinc ion battery and its MnO are related to2The preparation method of/C positive electrode material.The Zinc ion battery is made of anode, cathode, diaphragm and its electrolyte.Negative electrode material is based on Zn-ef ficiency, and it is solute, water for solvent that electrolyte, which is using soluble zinc salt and micro manganese salt, positive electrode MnO2/C.The preparation method prepares MnCO first with coprecipitation3Presoma, after the MnO of spinel structure is made by mixed calcining2/ C micron ball.The MnO that the method for the present invention obtains2/ C micron ball dispersion effect is good, and agglomeration and electric conductivity are obviously improved, and improves the cyclical stability of battery, forthright again and security performance, has very wide application prospect in the fields such as portable electronic product and power product.
Description
Technical field
The invention belongs to Zinc ion battery field, a kind of Zinc ion battery and its MnO are related to2The preparation of/C positive electrode material
Method.
Background technique
In recent years, with the development of economy with people to the exhaustive exploitation and benefit of the resources such as petroleum, coal, natural gas
With having resulted in the increasingly exhausted and environmental pollution of non-renewable resources.The energy and environment, which have become, hinders the world today
The problem of sustainable development.Therefore, it finds the green energy resource of substitution conventional fossil fuel and seeks the harmonious development of human and environment
Seem especially urgent.Due to Zinc ion battery because its divalent metal can increase the specific discharge capacity of battery system, also because of its tool
There are small size, low cost, aqueous electrolyte, green non-pollution, so making Zinc ion battery by extensive concern.Zinc ion
Battery is made of anode, cathode, electrolyte and diaphragm, just can extremely be embedded in the active material of zinc ion, cathode be zinc metal sheet or
Zinc powder, based on aqueous electrolyte, diaphragm is used to prevent the direct contact of positive and negative anodes and short circuit occurs electrolyte.
MnO2Have the characteristics that high power density and high-energy density, and coulombic efficiency as Zinc ion battery positive electrode
Close to 100%.In addition, manganese element nature rich reserves, environmentally protective, be used as Zinc ion battery electrode material have it is huge latent
Power.But MnO2Still remain electron conduction difference and Zn+Two problems of volume expansion occur in insertion abjection process, this obstruction
Its practical application in ion battery.In order to solve both of these problems, carbon coating is a kind of effectively approach.Uniformly
Carbon coating can effectively improve the electron conduction of material, Zn is effectively relieved+It is embedded in the volume expansion that abjection process occurs, from
And improve the cyclical stability and high rate performance of material.
105070901 A of Patent publication No CN has invented a kind of zinc lithium manganese aqoue seconary battery, but positive electrode manganese oxide
The volume change that the electric conductivity of lithium occurs with insertion abjection is not resolved, so as to cause poor cyclical stability and again
Rate performance.105375019 A of Patent publication No CN discloses a kind of Zinc ion battery positive electrode ZnMn2xCoxO4, cluster of grains
Poly- phenomenon is improved, but the electric conductivity of material does not solve still, and cyclical stability is poor, it is impossible to be used in actual production.
Summary of the invention
There are specific capacities it is an object of the invention to overcoming existing Zinc ion battery positive electrode low, cyclical stability and again
The disadvantage of forthright difference provides the preparation method of a kind of Rechargeable zinc ion battery and its positive electrode.
In order to achieve this, the technical solution adopted in the present invention is as follows:
1. a kind of Rechargeable zinc ion battery, including anode, cathode, electrolyte and diaphragm, negative electrode material is based on Zn-ef ficiency, electricity
It is solute, water for solvent that solution liquid, which is using soluble zinc salt and micro manganese salt, and diaphragm is pulp layered paper, Ni-Zn diaphragm, sulfonated membrane
And dust-free paper, positive electrode MnO2/C。
Negative electrode material described in above-mentioned steps 1 is zinc metal sheet or zinc powder, and positive electrode is MnO2/C。
Electrolyte described in above-mentioned steps 1 is the soluble zinc salt of 0.5 ~ 5mol/L and the manganese of 0.02 ~ 0.2mol/L
Salt, solvent are water.
Soluble zinc salt described in above-mentioned steps 1 can be zinc sulfate, zinc nitrate, zinc chloride and trifluoromethayl sulfonic acid
Zinc, manganese salt can be manganese sulfate, manganese nitrate, manganese chloride and trifluoromethayl sulfonic acid manganese.
Micro manganese salt can effectively improve the stable circulation of Zinc ion battery in electrolyte described in above-mentioned steps 1
Property.
Diaphragm described in above-mentioned steps 1 is one of pulp layered paper, Ni-Zn diaphragm, sulfonated membrane and dust-free paper or several
Kind, the puncture of cathode dendrite can be effectively prevent.
2. a kind of MnO2The preparation method of/C positive electrode material, which is characterized in that method includes the following steps:
(1) precursor preparation: being dissolved in 70ml deionized water for manganese salt and bicarbonate respectively, wherein the concentration of manganese salt be 0.01 ~
0.1mol/L, the solubility of bicarbonate are 0.1 ~ 1mol/L, and 3 ~ 10ml ethyl alcohol is then added into manganese salt.After being uniformly dispersed,
Two kinds of solution are mixed at room temperature and carry out coprecipitation reaction, after 1-5h, precipitating is centrifuged, wash, is dried, is obtained
MnCO3Presoma；
(2) mixed calcining: by the MnCO of preparation3Presoma is dispersed in the carbon source of 1mg/ml, uses Muffle furnace in inertia after dry
300 ~ 500 °C of calcining 2-10h, obtain the MnO of spinel structure under gas atmosphere2, heating rate is 1-10 °C/min；
The concentration of manganese salt described in above-mentioned steps (1) is 0.01 ~ 0.1mol/L, and the solubility of bicarbonate is 0.1 ~ 1mol/L,
The amount that ethyl alcohol is added is 3 ~ 10ml, reaction time 1-5h.
Manganese salt described in above-mentioned steps (1) is MnSO4Or MnCl2One of, bicarbonate NH4HCO3Or NaHCO3
One of.
Carbon source described in above-mentioned steps (2) is glucose, sucrose or maleic acid, and calcination temperature is 250 ~ 500 °C, calcining
Time is 2-10h, and heating rate is 1-10 °C/min.
Beneficial effects of the present invention: 1, the present invention relates to a kind of Zinc ion battery and its MnO2The preparation of/C positive electrode material
Method.The Zinc ion battery is made of anode, cathode, diaphragm and its electrolyte.Based on Zn-ef ficiency, electrolyte is negative electrode material
It is solvent, positive electrode MnO using soluble zinc salt and micro manganese salt as solute, water2/ C, works in coordination, and effectively increases
The cyclical stability of Zinc ion battery.2, the preparation method prepares MnCO first with coprecipitation3Presoma, after by with carbon source
Mixed calcining be made spinel structure MnO2/ C micron ball, improves electric conductivity, forthright again to be improved.3, institute of the present invention
Using preparation method, it is evenly coated, is simple process, portable strong.
Detailed description of the invention
Fig. 1 is MnO prepared by the present invention2/ C positive electrode material scanning electron microscope diagram piece.
Fig. 2 is MnO prepared by the present invention2/ C positive electrode material XRD spectrum.
Fig. 3 is the battery performance figure of example one to six.Current density is respectively 0.1A/g, 0.2A/g, 0.5A/g, 1A/g,
2A/g, each 5 circle.
Specific embodiment
The present invention provides a kind of Zinc ion battery and its MnO2The preparation method of/C positive electrode material, below with reference to embodiment
The present invention will be further described.
Embodiment one:
1. Zinc ion battery includes anode, cathode, electrolyte and diaphragm, negative electrode material is zinc metal sheet, and electrolyte is the sulphur of 3mol/L
Sour zinc adds the manganese sulfate of 0.1mol/L, and diaphragm is sulfonated membrane and two kinds of dust-free paper, positive electrode MnO2/C。
2. MnO2The preparation of/C positive electrode material:
(1) precursor preparation: by the MnSO of 0.05mol/L4With the NH of 0.5mol/L4HCO3It is dissolved in 70ml deionized water respectively, so
Backward MnSO47ml ethyl alcohol is added in solution.After being uniformly dispersed, two kinds of solution are mixed at room temperature and carry out coprecipitation reaction,
After 2h, precipitating is centrifuged, washed, is dried, MnCO is obtained3Presoma；
(2) mixed calcining: by the MnCO of preparation3Presoma is dispersed in the sucrose solution of 1mg/ml, is existed after dry with Muffle furnace
N2The lower 400 °C of calcinings 5h of atmosphere, obtains the MnO of spinel structure2/ C, heating rate are 5 °C/min；
Embodiment two:
1. Zinc ion battery includes anode, cathode, electrolyte and diaphragm, negative electrode material is zinc powder, and electrolyte is the nitre of 3mol/L
Sour zinc adds the manganese nitrate of 0.1mol/L, and diaphragm is two kinds of Ni-Zn diaphragm, positive electrode MnO2/C。
2. MnO2The preparation of/C positive electrode material:
(1) precursor preparation: by the MnCl of 0.1mol/L2With the NaHCO of 1mol/L3It is dissolved in 70ml deionized water respectively, then
To MnCl27ml ethyl alcohol is added in solution.After being uniformly dispersed, two kinds of solution are mixed at room temperature and carry out coprecipitation reaction, 2h
Afterwards, precipitating is centrifuged, washed, dried, obtain MnCO3Presoma；
(2) mixed calcining: by the MnCO of preparation3Presoma is dispersed in the glucose solution of 1mg/ml, uses Muffle furnace after dry
In N2The lower 400 °C of calcinings 2h of atmosphere, obtains the MnO of spinel structure2/ C, heating rate are 10 °C/min；
Embodiment three:
1. Zinc ion battery includes anode, cathode, electrolyte and diaphragm, negative electrode material is zinc metal sheet, and electrolyte is the three of 3mol/L
Fluoromethane sulfonic acid zinc adds the trifluoromethayl sulfonic acid manganese of 0.1mol/L, and diaphragm is sulfonated membrane and two kinds of dust-free paper, and positive electrode is
MnO2/C。
2. MnO2The preparation of/C positive electrode material:
(1) precursor preparation: by the MnSO of 0.05mol/L4With the NaHCO of 0.5mol/L3It is dissolved in 70ml deionized water respectively, so
Backward MnSO45ml ethyl alcohol is added in solution.After being uniformly dispersed, two kinds of solution are mixed at room temperature and carry out coprecipitation reaction,
After 5h, precipitating is centrifuged, washed, is dried, MnCO is obtained3Presoma；
(2) mixed calcining: by the MnCO of preparation3Presoma is dispersed in the maleic acid solution of 1mg/ml, uses Muffle furnace after dry
In N2The lower 300 °C of calcinings 3h of atmosphere, obtains the MnO of spinel structure2/ C, heating rate are 5 °C/min；
Example IV:
1. Zinc ion battery includes anode, cathode, electrolyte and diaphragm, negative electrode material is zinc powder, and electrolyte is the sulphur of 1mol/L
Sour zinc adds the manganese sulfate of 0.1mol/L, and diaphragm is pulp layered paper, positive electrode MnO2/C。
2. MnO2The preparation of/C positive electrode material:
(1) precursor preparation: by the MnCl of 0.1mol/L2With the NH of 1mol/L4HCO3It is dissolved in 70ml deionized water respectively, then
To MnCl210ml ethyl alcohol is added in solution.After being uniformly dispersed, two kinds of solution are mixed at room temperature and carry out coprecipitation reaction,
After 2h, precipitating is centrifuged, washed, is dried, MnCO is obtained3Presoma；
(2) mixed calcining: by the MnCO of preparation3Presoma is dispersed in the glucose solution of 1mg/ml, uses Muffle furnace after dry
400 °C of calcining 5h under an ar atmosphere, obtain the MnO of spinel structure2/ C, heating rate are 10 °C/min；
Embodiment five:
1. Zinc ion battery includes anode, cathode, electrolyte and diaphragm, negative electrode material is zinc metal sheet, and electrolyte is the three of 1mol/L
Fluoromethane sulfonic acid zinc adds the trifluoromethayl sulfonic acid manganese of 0.1mol/L, and diaphragm is sulfonated membrane and two kinds of pulp layered paper, and positive electrode is
MnO2/C。
2. MnO2The preparation of/C positive electrode material:
(1) precursor preparation: by the MnSO of 0.05mol/L4With the NH of 0.5mol/L4HCO3It is dissolved in 70ml deionized water respectively, so
Backward MnSO45ml ethyl alcohol is added in solution.After being uniformly dispersed, two kinds of solution are mixed at room temperature and carry out coprecipitation reaction,
After 2h, precipitating is centrifuged, washed, is dried, MnCO is obtained3Presoma；
(2) mixed calcining: by the MnCO of preparation3Presoma is dispersed in the sucrose solution of 1mg/ml, is existed after dry with Muffle furnace
N2The lower 500 °C of calcinings 5h of atmosphere, obtains the MnO of spinel structure2/ C, heating rate are 5 °C/min；
Embodiment six:
1. Zinc ion battery includes anode, cathode, electrolyte and diaphragm, negative electrode material is zinc metal sheet, and electrolyte is the three of 1mol/L
Fluoromethane sulfonic acid zinc adds the trifluoromethayl sulfonic acid manganese of 0.1mol/L, and diaphragm is dust-free paper, positive electrode MnO2/C。
2. MnO2The preparation of/C positive electrode material:
(1) precursor preparation: by the MnSO of 0.05mol/L4With the NH of 0.5mol/L4HCO3It is dissolved in 70ml deionized water respectively, so
Backward MnSO410ml ethyl alcohol is added in solution.After being uniformly dispersed, two kinds of solution are mixed at room temperature and be co-precipitated instead
It answers, after 5h, precipitating is centrifuged, wash, is dried, MnCO is obtained3Presoma；
(2) mixed calcining: by the MnCO of preparation3Presoma is dispersed in the maleic acid solution of 1mg/ml, uses Muffle furnace after dry
In N2The lower 250 °C of calcinings 5h of atmosphere, obtains the MnO of spinel structure2/ C, heating rate are 10 °C/min.
Claims (10)
1. a kind of Rechargeable zinc ion battery, including anode, cathode, electrolyte and diaphragm, negative electrode material is based on Zn-ef ficiency, electricity
It is solute, water for solvent that solution liquid, which is using soluble zinc salt and micro manganese salt, and diaphragm is pulp layered paper, Ni-Zn diaphragm, sulfonated membrane
And dust-free paper, positive electrode MnO2/C。
2. a kind of Rechargeable zinc ion battery according to claim 1, which is characterized in that negative electrode material is zinc metal sheet or zinc
Powder, positive electrode are MnO2/C。
3. a kind of Rechargeable zinc ion battery according to claim 1, which is characterized in that electrolyte is 0.5 ~ 5mol/L
Soluble zinc salt and 0.02 ~ 0.2mol/L manganese salt, solvent is water.
4. a kind of Rechargeable zinc ion battery according to claim 1, which is characterized in that soluble zinc salt can be sulfuric acid
Zinc, zinc nitrate, zinc chloride and trifluoromethayl sulfonic acid zinc, manganese salt can be manganese sulfate, manganese nitrate, manganese chloride and trifluoromethayl sulfonic acid
Manganese.
5. a kind of Rechargeable zinc ion battery according to claim 1, which is characterized in that micro manganese salt can in electrolyte
To effectively improve the cyclical stability of Zinc ion battery.
6. a kind of Rechargeable zinc ion battery according to claim 1, which is characterized in that diaphragm be pulp layered paper, Ni-Zn every
One or both of film, sulfonated membrane and dust-free paper.
7. a kind of MnO2The preparation method of/C positive electrode material, which is characterized in that method includes the following steps:
(1) precursor preparation: being dissolved in 70ml deionized water for manganese salt and bicarbonate respectively, wherein the concentration of manganese salt be 0.01 ~
0.1mol/L, the solubility of bicarbonate are 0.1 ~ 1mol/L, and 3 ~ 10ml ethyl alcohol is then added into manganese salt, after being uniformly dispersed,
Two kinds of solution are mixed at room temperature and carry out coprecipitation reaction, after 1-5h, precipitating is centrifuged, wash, is dried, is obtained
MnCO3Presoma；
(2) mixed calcining: by the MnCO of preparation3Presoma is dispersed in the carbon source of 1mg/ml, uses Muffle furnace in indifferent gas after dry
300 ~ 500 °C of calcining 2-10h, obtain the MnO of spinel structure under body atmosphere2, heating rate is 1-10 °C/min.
8. a kind of MnO according to claim 62The preparation method of/C positive electrode material, which is characterized in that in step (1), manganese
The concentration of salt is 0.01 ~ 0.1mol/L, and the solubility of bicarbonate is 0.1 ~ 1mol/L, and the amount that ethyl alcohol is added is 3 ~ 10ml, reaction
Time is 1-5h.
9. a kind of MnO according to claim 62The preparation method of/C positive electrode material, which is characterized in that in step (1), manganese
Salt is MnSO4Or MnCl2One of, bicarbonate NH4HCO3Or NaHCO3One of.
10. a kind of MnO according to claim 62The preparation method of/C positive electrode material, which is characterized in that in step (2), carbon
Source be glucose, sucrose or maleic acid, calcination temperature be 250 ~ 500 °C, calcination time 2-10h, heating rate be 1-10 °C/
min。
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