CN102013527A - Rechargeable zinc ion battery - Google Patents
Rechargeable zinc ion battery Download PDFInfo
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- CN102013527A CN102013527A CN2009102056405A CN200910205640A CN102013527A CN 102013527 A CN102013527 A CN 102013527A CN 2009102056405 A CN2009102056405 A CN 2009102056405A CN 200910205640 A CN200910205640 A CN 200910205640A CN 102013527 A CN102013527 A CN 102013527A
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- zinc
- ion battery
- zinc ion
- chargeable
- collector
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- 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
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Abstract
The invention discloses a rechargeable zinc ion battery. An active material of the anode of the battery is a nonmetal doped manganese dioxide material, the cathode is mainly made of zinc element, and an electrolyte is a liquid or gel electrolyte using soluble salt as a solute and water as a solvent and having ionic conductivity. The invention utilizes the energy storage mechanism that zinc ions (Zn2+) are reversibly inserted or removed from lattices of the anode material and the cathode material mainly comprising the zinc element is used for oxidization or zinc ions (Zn2+) are reduced on the surface of the cathode, and meanwhile, the battery has the characteristics of high capacity and quick charge capability.
Description
Technical field
The invention belongs to the battery technology field, be specifically related to a kind of zinc ion and take off embedding and at the chargeable zinc ion battery of negative pole reduction or oxidation at positive electrode active materials.
Background technology
Along with constant development of economy, must cause the scarcity of petroleum resources and the pollution of environment, so the development and utilization of the comprehensive high-efficiency of new green power has become very necessary problem.The primary cell of comparing, secondary cell can repeat repeatedly to carry out charge and discharge cycles, can make full use of raw material, so its more economical practicality.The most famous rechargeable battery (secondary cell) is a lithium ion battery.Lithium ion battery is to utilize Li
+Ion comes store electrical energy as energy-accumulating medium, and it utilizes Li
+Positive pole and negative material that ion can embed or deviate from, lithium ion is deviate from the interlayer that is embedded into negative pole (being generally graphite) through electrolyte then from positive electrode when charging; When discharge, the lithium ion that is embedded into graphite cathode is deviate from by electrolyte to move to positive pole again from negative pole, therefore can liken lithium ion battery to a rocking chair visually, the two ends of rocking chair are the both positive and negative polarity of battery, and lithium ion makes little runs to and fro at the two ends of rocking chair, so lithium ion battery also is lithium ion rocking chair battery (Rocking chair battery).Along with increase and the kind of mobile electronic product and the continuous growth of quantity of mankind's activity, will constantly increase the demand of secondary cell, so the development of new rechargeable battery is very necessary and important.
We have found divalent zinc ion (Zn first in nearest research
2+) the reversible embedding and the behavior of deviating from manganese bioxide material, and be accompanied by Mn
4+/ Mn
3+Reversible appraising at the current rate store and discharge electronics (electric energy):
xZn
2++2xe
-+MnO
2＝Zn
xMnO
2 (1)
The embedding behavior of this zinc ion has the capacity height, characteristics such as good reversibility and cycle-index are many, on the basis of this research, we are anodal with manganese dioxide, with zinc is negative pole, form a kind of brand-new filled Zinc ion battery with the electrolyte that contains zinc ion, when charging zinc ion deviate from the manganese dioxide tunnel and deposit at negative pole then through electrolyte, negative pole zinc is dissolved as zinc ion and is embedded in the tunnel of manganese dioxide positive pole material through electrolyte during discharge, therefore can also liken this Zinc ion battery to the rocking chair battery, the two ends of rocking chair are the both positive and negative polarity of battery, [Kang Feiyu becomes pretty Du Hong to reach Li Baohua slowly and zinc ion makes little runs to and fro at the two ends of rocking chair, a kind of chargeable zinc ion battery, application number: 200910106650.3].
The mechanism of this Zinc ion battery stored electrons is as follows:
Anodal: δ Zn
2++ 2 δ e+MnO
2=Zn
δMnO
2(2)
Negative pole: Zn=Zn
2++ 2e (3)
Take off the embedding behavior owing to use zinc ion positive electrode reversible, therefore this battery that fills zinc ion has the capacity height, and characteristics such as have extended cycle life.
Nearest discovers, also can store and discharge zinc ion in the neutral aqueous solution with the manganese dioxide of nonmetal doping, therefore, the manganese dioxide that this patent proposes with nonmetal doping is positive pole, zinc or kirsite are negative pole, and the neutral aqueous solution that contains zinc ion is a kind of Zinc ion battery that fills of electrolyte.
Summary of the invention
The secondary cell that the objective of the invention is to propose a kind of energy density height, power density height, has extended cycle life.
The present invention proposes a kind of chargeable zinc ion battery, is made up of positive pole, negative pole, marginal barrier film and the electrolyte that contains zwitterion and have an ionic conductivity, it is characterized in that:
Described negative pole adopts the active material based on zinc element,
Positive electrode active materials is the nonmetal doping manganese bioxide material,
Described electrolyte is that the soluble-salt with zinc is that solute, water are solvent and liquid state with ionic conductivity or gel state material, and the pH value is between 3～7.
The chargeable zinc ion battery that the present invention proposes is characterized in that: the nonmetal doping manganese dioxide that constitutes positive electrode active materials is MnO
2-xA
x, wherein, A is F, Cl, S, N, P, Br or I element, 0＜x≤0.4.
The chargeable zinc ion battery that the present invention proposes, it is characterized in that: described positive pole comprises the MnO that uses on collector and the collector
2-xA
xWith the film material that binding agent is made, wherein, A is F, Cl, S, N, P, Br or I element, 0＜x≤0.4.
The chargeable zinc ion battery that the present invention proposes, it is characterized in that: described negative pole is the alloy of simple metal zinc or zinc.
The chargeable zinc ion battery that the present invention proposes, it is characterized in that: described negative pole comprises the active material based on zinc powder on collector and the collector, this active material is the film material made from zinc powder and binding agent.
The chargeable zinc ion battery that the present invention proposes is characterized in that: comprise also in the negative active core-shell material that electron conduction agent, the addition of electron conduction agent are below 50% of negative electrode film quality.
The chargeable zinc ion battery that the present invention proposes, it is characterized in that: the soluble-salt of described zinc is zinc nitrate, zinc sulfate or zinc chloride.
A kind of chargeable zinc ion battery that the present invention proposes is characterized in that: described negative material can be for containing and based on the membranaceous of zinc powder or paste material.
A kind of chargeable zinc ion battery that the present invention proposes, it is characterized in that: the additive that contains electron conduction agent, binding agent, oxide powder and zinc (ZnO) in the film material of described negative material based on zinc powder or have specific function, wherein the electron conduction agent is graphite, carbon black, acetylene black, charcoal fiber, carbon nano-fiber or carbon nanotube, and addition is below 50% of negative electrode film quality; Binding agent is polytetrafluoroethylene, water-soluble rubber, poly-inclined to one side tetrafluoroethene or cellulose, and addition is below 20% of negative electrode film quality; The addition of zinc oxide is below 50% of negative electrode film quality.
A kind of chargeable zinc ion battery that the present invention proposes is characterized in that: the additive that also contains electrolyte, thickener, oxide powder and zinc and have specific function in the paste material of described negative material based on zinc powder.Electrolyte is mainly and contains zinc ion (Zn
2+) the aqueous solution, its addition is below 40% of negative electrode film quality; Thickener is mainly ester class or carboxylic acids etc., and as polyacrylic acid, Sodium Polyacrylate etc., its addition is below 10% of negative electrode film quality, and the addition of zinc oxide is below 50% of negative electrode film quality.
A kind of chargeable zinc ion battery that the present invention proposes, it is characterized in that: the additive with specific function that contains in the described negative pole is for restraining or eliminate the corrosion inhibiter of zinc element evolving hydrogen reaction, can be oxide or hydroxide, the metallic copper etc. of indium, its addition is below 1% of negative electrode film quality.
A kind of chargeable zinc ion battery that the present invention proposes, it is characterized in that: except active material, also contain electron conduction agent, binding agent etc. in the described positive pole, wherein the electron conduction agent is graphite, carbon black, acetylene black, charcoal fiber or carbon nanotube, and addition is below 50% of cathode film quality; Binding agent is polytetrafluoroethylene, water-soluble rubber, poly-inclined to one side tetrafluoroethene or cellulose, and addition is below 20% of cathode film quality.
A kind of chargeable zinc ion battery that the present invention proposes, it is characterized in that: described battery structure can be button, column type or square structure.
Rechargeable battery of the present invention utilizes zinc ion (Zn
2+) in the positive electrode lattice reversible insertion or deviate from, simultaneously the negative material based on zinc element carries out oxidation or zinc ion (Zn
2+) in the energy storage mechanism of negative terminal surface reduction, and adopted special electrolyte, this battery to have the characteristics of the high and quickly-chargeable of capacity.
It does positive electrode active materials with nonmetal doping manganese bioxide material (changing the structure and the electronic structure characteristic of former manganese bioxide material), the filled Zinc ion battery that available can be good, and the filled Zinc ion battery that experiment makes is at 0.1A g
-1Under (with the positive active material Mass Calculation) constant current first discharge capacity can reach 165mAh/g, and through ten times the circulation, capacity still is 150mAh/g, cycle life is good.This chargeable zinc ion battery can be predicted and fields such as individual digital notepad, Blectronic Organizers, mobile phone, cordless telephone, beeper, electronic toy, game machine, portable data terminals, personal audio video-unit, experimental provision, palmtop computer can be widely used in.
Description of drawings
Among Fig. 1 embodiment 1 with MnO
1.8F
0.2The Zinc ion battery charging and discharging curve that the 11st to 21 time circulates under the 0.1A/g constant current for positive pole.
Embodiment
Embodiment 1:
With MnO
1.8F
0.2, conductive agent acetylene black and polyfluortetraethylene of binding element be coated on the stainless steel foil after mixing with 7: 2: 1 mass ratio, be cut into a certain size, oven dry is negative pole for the positive electrical pole piece with zinc paper tinsel (0.1mm is thick) in vacuum, and electrolyte is that the pH value is 4.2 1mol L
-1ZnSO
4The aqueous solution is assembled into button cell.This Zinc ion battery is at 50mA g
-1Under (with the positive active material Mass Calculation) constant current first discharge capacity be 160mAh/g, through ten times the circulation, capacity still is 132mAh/g.As seen, with MnO
1.8F
0.2The discharge capacity first of the filled Zinc ion battery that makes for positive active material is big, and cycle life is good.
Embodiment 2:
With MnO
1.7Cl
0.3, conductive agent acetylene black and polyfluortetraethylene of binding element be coated on the stainless steel foil after mixing with 7: 2: 1 mass ratio, be cut into a certain size, oven dry is negative pole for the positive electrical pole piece with zinc paper tinsel (0.1mm is thick) in vacuum, and electrolyte is that the pH value is 6.2 1mol L
-1ZnSO
4The aqueous solution is assembled into button cell.This Zinc ion battery is at 50mA g
-1Under (with the positive active material Mass Calculation) constant current first discharge capacity be 155mAh/g, through ten times the circulation, capacity still is 120mAh/g.
Embodiment 3:
With MnO
1.9S
0.1, conductive agent acetylene black and polyfluortetraethylene of binding element be coated on the stainless steel foil after mixing with 7: 2: 1 mass ratio, be cut into a certain size, oven dry is the positive electrical pole piece in vacuum, be coated on stainless steel foil after mixing with 70: 20: 10 mass ratio with zinc powder, conduction charcoal, polyfluortetraethylene of binding element, be cut into a certain size, oven dry is negative pole in the vacuum, and electrolyte is that the pH value is 5 1mol L
-1ZnSO
4The aqueous solution is assembled into button cell.This Zinc ion battery is at 0.1A g
-1Under (with the positive active material Mass Calculation) constant current first discharge capacity be 165mAh/g, through ten times the circulation, capacity still is 150mAh/g.
Claims (10)
1. chargeable zinc ion battery is made up of positive pole, negative pole, marginal barrier film and the electrolyte that contains zwitterion and have an ionic conductivity, it is characterized in that:
Described negative pole adopts the active material based on zinc element,
Positive electrode active materials is the nonmetal doping manganese bioxide material,
Described electrolyte is that the soluble-salt with zinc is that solute, water are solvent and liquid state with ionic conductivity or gel state material, and the pH value is between 3～7.
2. chargeable zinc ion battery according to claim 1 is characterized in that: the nonmetal doping manganese bioxide material that constitutes positive electrode active materials is MnO
2-xA
x, wherein, doped chemical A is F, Cl, S, N, P, Br or I element, 0＜x≤0.4.
3. chargeable zinc ion battery according to claim 1 is characterized in that: described positive pole comprises the MnO that uses on collector and the collector
2-xA
xWith the film material that binding agent is made, wherein, A is F, Cl, S, N, P, Br or I element, 0＜x≤0.4.
4. chargeable zinc ion battery according to claim 1 is characterized in that: described positive pole comprises the cathode film on collector and the collector, cathode film MnO
2-xA
x, electron conduction agent and binding agent make, wherein, A is F, Cl, S, N, P, Br or I element, 0＜x≤0.4, the addition of electron conduction agent is below 50% of cathode film quality, the addition of binding agent is below 20% of cathode film quality.
5. chargeable zinc ion battery according to claim 1 is characterized in that: described negative pole is the alloy of simple metal zinc or zinc.
6. chargeable zinc ion battery according to claim 1 is characterized in that: described negative pole comprises the active material based on zinc powder on collector and the collector, and this active material is the film material made from zinc powder and binding agent.
7. chargeable zinc ion battery according to claim 6, it is characterized in that: also comprise corrosion inhibiter and/or electron conduction agent in the negative active core-shell material, the addition of corrosion inhibiter is below 1% of negative electrode film quality, and the addition of electron conduction agent is below 50% of negative electrode film quality.
8. chargeable zinc ion battery according to claim 7 is characterized in that: the electron conduction agent is graphite, carbon black, acetylene black, charcoal fiber, carbon nano-fiber or carbon nanotube, and corrosion inhibiter is the oxide of indium, the hydroxide or the copper of indium.
9. chargeable zinc ion battery according to claim 1, it is characterized in that: described negative pole comprises the paste active material based on zinc powder on collector and the collector, this paste active material comprises zinc powder, electrolyte, thickener, oxide powder and zinc and corrosion inhibiter, electrolyte is the aqueous solution that contains zinc ion, its addition is below 40% of negative electrode film quality, the addition of thickener is below 10% of negative electrode film quality, the addition of zinc oxide is below 50% of negative electrode film quality, and the addition of corrosion inhibiter is below 1% of negative electrode film quality.
10. according to each described chargeable zinc ion battery of claim 1-9, it is characterized in that: the soluble-salt of described zinc is zinc nitrate, zinc sulfate or zinc chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102056405A CN102013527B (en) | 2009-09-08 | 2009-09-30 | Rechargeable zinc ion battery |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910190012 | 2009-09-08 | ||
| CN200910190010.5 | 2009-09-08 | ||
| CN200910190010 | 2009-09-08 | ||
| CN200910190012.4 | 2009-09-08 | ||
| CN2009102056405A CN102013527B (en) | 2009-09-08 | 2009-09-30 | Rechargeable zinc ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102013527A true CN102013527A (en) | 2011-04-13 |
| CN102013527B CN102013527B (en) | 2012-08-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2009101797227A Active CN102013526B (en) | 2009-09-08 | 2009-09-30 | Rechargeable zinc ion battery |
| CN2009102056405A Expired - Fee Related CN102013527B (en) | 2009-09-08 | 2009-09-30 | Rechargeable zinc ion battery |
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| CN103117384A (en) * | 2012-11-09 | 2013-05-22 | 湘潭大学 | Anion X-doped lambda-MnO2 lithium primary battery positive electrode material and preparation method thereof |
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| CN107910525A (en) * | 2017-11-16 | 2018-04-13 | 中山大学 | A kind of preparation method of N doping manganese carbonate and its compound |
| CN111977695A (en) * | 2020-08-27 | 2020-11-24 | 陕西科技大学 | Preparation of N3-Ion-doped MnO2Method for preparing lithium ion battery cathode material |
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| WO1998031063A1 (en) * | 1997-01-09 | 1998-07-16 | Sanyo Electric Co., Ltd. | Alkaline storage battery and method for charging battery |
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| KR20000001242A (en) * | 1998-06-10 | 2000-01-15 | 이병길 | Secondary cell with zinc sulfate aqueous solution |
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| CN101373829B (en) * | 2008-10-07 | 2011-05-11 | 深圳市贝特瑞新能源材料股份有限公司 | Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery |
-
2009
- 2009-09-30 CN CN2009101797227A patent/CN102013526B/en active Active
- 2009-09-30 CN CN2009102056405A patent/CN102013527B/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CN102013527B (en) | 2012-08-29 |
| CN102013526B (en) | 2012-08-29 |
| CN102013526A (en) | 2011-04-13 |
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