CN107221716A - A kind of chargeable water system Zinc ion battery - Google Patents
A kind of chargeable water system Zinc ion battery Download PDFInfo
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- CN107221716A CN107221716A CN201710369663.4A CN201710369663A CN107221716A CN 107221716 A CN107221716 A CN 107221716A CN 201710369663 A CN201710369663 A CN 201710369663A CN 107221716 A CN107221716 A CN 107221716A
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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
- H01M10/38—Construction or manufacture
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to mechanism of new electrochemical power sources and new energy materialses field, specifically related to a kind of new chargeable water system Zinc ion battery by electrode active material of vanadate, it is made up of positive pole, negative pole, the barrier film fallen between and the electrolyte containing zwitterion and with ionic conductivity, the active material of described positive pole is based on the vanadate of deintercalation zinc ion；The electrolyte is that the soluble-salt of zinc is that solute, water are solvent, and concentration is 0.1-5mol/L, liquid or gel state material with ionic conductivity.Water system Zinc ion battery is assembled into, the material shows excellent high rate capability, cyclical stability and long-life, is the potential application material of high power, long-life Zinc ion battery, has broad application prospects in terms of extensive energy storage.
Description
Technical field
The invention belongs to mechanism of new electrochemical power sources and new energy materialses field, and in particular to one kind is using vanadate as electrode activity
The new chargeable water system Zinc ion battery of material.
Background technology
The development and utilization of green clean energy resource has important for the energy crisis that solution current mankind society is faced
Meaning.Novel energy such as solar energy, wind energy etc. are because gradually being received and being promoted by the world the advantages of its is renewable, pollution-free.
But these energy conversions are into must need after electric energy the electric power storage devices of efficient, reusable edible to meet consumer couple
The requirement of portable electronic articles.In this context, the development attention of battery.One-shot battery, such as nickel-cadmium cell, ni-mh electricity
Pond and lead-acid battery etc. are low because of its specific capacity, and cycle life is short, and the charging interval is long, there is that pollution limits its to environment
Using.Lithium rechargeable battery because its have high operating voltage, larger specific energy, the cycle life of length, memory-less effect,
The performance such as environmentally friendly, has become the primary study object of scientific researcher, and is increasingly widely applied.So
And, there are problems that limiting during limited lithium resource, increasingly increased production cost and use its
The application in large-scale energy storage field.
As new century another important green energy storage device, Zinc ion battery is because of its distinctive low cost, safety, ring
Protect etc. advantage and be widely deployed and study.However, the relatively low energy density of Zinc ion battery, longer charging interval and shorter
Cycle life limit its development space.Develop the high-performance based on nano material, Composite, low cost, the zinc of greenization
Ion battery is intersection and the forward position of new energy technology and nanometer technology, with important scientific meaning and potential using value.
And the performance of Zinc ion battery depends greatly on electrode material, therefore, research and development low cost, high power capacity, length
The electrode material in life-span is to promote the fast-developing and wide variety of key of Zinc ion battery.
The content of the invention
It is an object of the invention to provide a kind of safety and environmental protection, cost is low, while having high-energy-density and long circulation life
Chargeable water system Zinc ion battery.
The present invention solves the technical scheme that is used of above-mentioned technical problem：A kind of chargeable water system Zinc ion battery, by
Positive pole, negative pole, the barrier film fallen between and the electrolyte composition containing zwitterion and with ionic conductivity, it is described
Positive pole active material for deintercalation zinc ion vanadate based on；The electrolyte is that the soluble-salt of zinc is that solute, water are
Solvent, concentration is 0.1-5mol/L, liquid or gel state material with ionic conductivity.
By such scheme, described vanadate molecular formula is AxVyOz, wherein, A=Li, Na, K or Rb；0<x<20,0<y<
20,0<z<20.
By such scheme, described x=0.33, y=2, z=5.
By such scheme, the barrier film be the fibreglass diaphragm with excellent wellability, filter paper or polytetrafluoroethylene (PTFE) every
Film.
By such scheme, the active material of described negative pole uses metal zinc metal sheet, zinc powder or zinc carbon complex.
By such scheme, the soluble-salt of described zinc is trifluoromethayl sulfonic acid zinc, zinc perchlorate or zinc sulfate.
By such scheme, the additive in described electrolyte is the soluble-salt containing vanadium.
Present invention firstly discovers that zinc ion can be reversible in vanadate materials A in aqueous electrolytexVyOzIt is middle to be taken off
Embedding, this Zinc ion battery has safety and environmental protection, and cost is low, and capacity is high, the characteristics of cyclicity is good.The positive plate of the present invention can be with
Scheme is prepared using following：Binding agent is dissolved in corresponding reagent, a certain amount of vanadic acid salt material and conductive agent are ground uniform
After add in above-mentioned solution, carry out point ultrasound dissipate, be prepared into slurry, be evenly applied on collector, coat thickness be 50-
250 μm, positive plate is made in vacuum drying.The collector include carbon cloth, nickel foam, stainless steel foil, copper foil, aluminium foil, molybdenum foil and
Titanium foil；The conductive agent includes activated carbon, Carbon fibe, acetylene black, Ketjen black, graphite carbon nanotube；The binding agent is poly- inclined
PVF (PVDF), polytetrafluoroethylene (PTFE) (PTFE) or sodium carboxymethylcellulose (CMC)；The negative plate of the present invention can use as follows
Preparation scheme：Wherein metal zinc metal sheet is polished with sand paper, is cleaned with alcohol and acetone several times, directly as negative plate；Using zinc powder
When, it is necessary to uniform with conductive agent grinding, be uniformly mixed and made into slurry with adhesive, be coated on the afflux that thickness is 0.01-1.0mm
On body, coat thickness is 1-250 μm, and negative plate is made in vacuum drying；The electrolyte of the present invention is with fluoroform sulphur
Sour zinc, double trifluoromethanesulfonimides, zinc perchlorate, zinc sulfate are that solute, water are solvent, liquid with ionic conductivity or
Gel state material；Wherein, the concentration of electrolyte is that the additive in 0.1-5mol/L, electrolyte is the soluble-salt containing vanadium.Can
By adding the pH value to adjust electrolyte such as acid, alkali or cushioning liquid 2~7.5.
The beneficial effects of the invention are as follows：Can be reversible in vanadate materials A in aqueous electrolyte using zinc ionxVyOz
(wherein, A=Li, Na, K, Rb；0<x<20,0<y<20,0<z<20) deintercalation is carried out in, while the negative pole based on zinc is water-soluble
There is the energy storage mechnism of stable redox reaction, this kind of battery has cyclicity good, the characteristics of capacity is high in liquid.Synthesize vanadium
Hydrochlorate electrode material is low for equipment requirements, simple for process, and the operation cycle is short, it is easy to extension production；Electrolyte is employed
Water system trifluoromethayl sulfonic acid zinc, double trifluoromethanesulfonimides, zinc perchlorate, zinc sulphate electrolyte, with cheap, safety
The advantage of environmental protection；Meanwhile, negative pole uses aboundresources, cheap Zinc material.Water system Zinc ion battery is assembled into, material performance
Go out excellent high rate capability, cyclical stability and long-life, be the potential application material of high power, long-life Zinc ion battery
Material, has broad application prospects in terms of extensive energy storage.
Brief description of the drawings
Fig. 1 is the Na of the embodiment of the present invention 10.33V2O5The XRD of nano-material；
Fig. 2 is the Na of the embodiment of the present invention 10.33V2O5In 0.2Ag-1Cycle performance of battery curve map under current density；
Fig. 3 is the button cell that the embodiment of the present invention 2 is assembled；
Fig. 4 is the Li of the embodiment of the present invention 20.33V2O5The high rate performance figure of material；
Fig. 5 is the flexible-packed battery that the embodiment of the present invention 3 is assembled；
Fig. 6 is the Na of the embodiment of the present invention 30.33V2O5Material in 1.0Ag-1Cycle performance of battery under current density is bent
Line chart.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1：
A kind of Rechargeable zinc ion battery of long-life high-energy-density, positive active material uses Na0.33V2O5Nano wire
Material (XRD is Fig. 1), negative pole is that, using zinc metal sheet as material, barrier film uses fibreglass diaphragm, and electrolyte is 3mol/L fluoroforms
Sulfonic acid zinc.Its preparation method, comprises the following steps：
(1)Na0.33V2O5The preparation of positive plate
It will be obtained in binding agent polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE) (PTFE) molten 1-METHYLPYRROLIDONE (NMP)
To settled solution, by a certain amount of Na0.33V2O5Added after the grinding of nanowire positive electrode material is uniform in above-mentioned solution and (press active matter
Matter：Acetylene black：Bonding agent=7:2:1), carry out a point ultrasound to dissipate, be prepared into slurry, be evenly applied to the titanium foil that thickness is 0.05mm
On, coat thickness is 150 μm, and positive plate is made in vacuum drying.
(2) preparation of electrolyte
A certain amount of trifluoromethayl sulfonic acid zinc salt is dissolved in deionized water, the electrolyte that concentration is 3mol/L is configured to；
(3) preparation of negative plate
Metal zinc metal sheet is polished with sand paper, cleaned with alcohol and acetone several times, punching obtains a diameter of 12mm disk, is made
For negative plate.
(4) assembling of water system Zinc ion battery
The glass fibre that the negative plate that the positive plate that step (1) is prepared is prepared with step (3) is 0.2mm with thickness
Film is separated, and is put into battery case, is then injected separately into the sulfuric acid zinc salt that concentration is 3mol/L, finally battery is packaged.
Nano-material prepared by embodiment 1, X-ray diffraction analysis are shown as pure phase Na0.33V2O5, as shown in Figure 1.Make
For Zinc ion battery positive electrode active materials, excellent chemical property is shown.As shown in Fig. 2 being 0.2Ag in current density-1
Shi Jinhang constant current charge-discharge tests, discharge capacity is respectively 276.6mAh g-1, after 100 circulations, capability retention is
91.3%.The water system Zinc ion battery not only has high specific capacity and long cycle life, also simple with technique, safety collar
Protect, the low advantage of cost has broad application prospects in terms of extensive energy storage.
Embodiment 2：
A kind of Rechargeable zinc ion battery of long-life high-energy-density, positive active material uses Li0.33V2O5Nano wire
Material, negative pole is that, using zinc metal sheet as material, barrier film uses fibreglass diaphragm, and electrolyte is 3mol/L zinc sulfate.Preparation method, bag
Include following steps：
(1)Li0.33V2O5The preparation of positive plate
It will be obtained in binding agent polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE) (PTFE) molten 1-METHYLPYRROLIDONE (NMP)
To settled solution, by a certain amount of Li0.33V2O5Added after material grinding is uniform in above-mentioned solution and (press active material：Acetylene black：
Bonding agent=7:2:1), carry out a point ultrasound to dissipate, be prepared into slurry, be evenly applied on the titanium foil that thickness is 0.05mm, coat
Thickness is 150 μm, and positive plate is made in vacuum drying.
(2) preparation of electrolyte
A certain amount of sulfuric acid zinc salt is dissolved in deionized water, the electrolyte that concentration is 3mol/L is configured to.
(3) preparation of negative plate
Metal zinc metal sheet is polished with sand paper, cleaned with alcohol and acetone several times, punching obtains a diameter of 12mm disk, is made
For negative plate.
(4) assembling of water system Zinc ion battery
The glass fibre that the negative plate that the positive plate that step (1) is prepared is prepared with step (3) is 0.2mm with thickness
Film is separated, and is put into battery case, is then injected separately into the sulfuric acid zinc salt that concentration is 3mol/L, is finally packaged into button cell, such as
Shown in Fig. 3.
Li prepared by embodiment 20.33V2O5Nano-material is shown excellent as Zinc ion battery positive electrode active materials
Chemical property.As shown in figure 4, being 0.1,0.2,0.5,0.8,1.0 and 2.0Ag in current density-1Shi Jinhang constant current charge and discharges
Electrical testing, discharge capacity is respectively 362.2,254.6,172.5,141.7,138.2 and 100.4mA h g-1, show excellent
High rate performance.
Embodiment 3：
A kind of Rechargeable zinc ion battery of long-life high-energy-density, positive active material uses Na0.33V2O5Nano wire
Material, negative pole is that, using zinc metal sheet as material, barrier film uses fibreglass diaphragm, and electrolyte is 3mol/L zinc sulfate.Preparation method, bag
Include following steps：
(1)Na0.33V2O5The preparation of positive plate
It will be obtained in binding agent polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE) (PTFE) molten 1-METHYLPYRROLIDONE (NMP)
To settled solution, by a certain amount of Na0.33V2O5Added after material grinding is uniform in above-mentioned solution and (press active material：Acetylene black：
Bonding agent=7:2:1), carry out a point ultrasound to dissipate, be prepared into slurry, be evenly applied on the titanium foil that thickness is 0.05mm, coat
Thickness is 150 μm, and positive plate is made in vacuum drying.
(2) preparation of electrolyte
A certain amount of sulfuric acid zinc salt is dissolved in deionized water, the electrolyte that concentration is 3mol/L is configured to, wherein also adding
Plus 0.01mol/L oxygen vanadium sulphate solutions.
(3) preparation of negative plate
Metal zinc metal sheet is polished with sand paper, cleaned with alcohol and acetone several times, punching obtains a diameter of 12mm disk, is made
For negative plate.
(4) assembling of water system Zinc ion battery
The glass fibre that the negative plate that the positive plate that step (1) is prepared is prepared with step (3) is 0.2mm with thickness
Film is separated, and is put into battery case, is then injected separately into the sulfuric acid zinc salt that concentration is 3mol/L, is finally packaged into flexible-packed battery,
As shown in Figure 5.
Na prepared by embodiment 30.33V2O5Nano-material is shown excellent as Zinc ion battery positive electrode active materials
Chemical property.As shown in fig. 6, in 1.0Ag-1Current density under tested, circulation 1000 times after, specific discharge capacity can
Up to 212.4mAh g-1, capability retention be higher than 92%, show excellent cycle performance.
Claims (7)
1. a kind of chargeable water system Zinc ion battery, by positive pole, negative pole, the barrier film fallen between and contain zwitterion
And the electrolyte with ionic conductivity is constituted, the active material of described positive pole is based on the vanadate of deintercalation zinc ion；Institute
It is that solute, water are solvent to state the soluble-salt that electrolyte is zinc, and concentration is 0.1-5mol/L, liquid with ionic conductivity or
Gel state material.
2. chargeable water system Zinc ion battery according to claim 1, it is characterised in that：Described vanadate molecular formula is
AxVyOz, wherein, A=Li, Na, K or Rb；0<x<20,0<y<20,0<z<20.
3. chargeable water system Zinc ion battery according to claim 2, it is characterised in that：Described x=0.33, y=2, z
=5.
4. chargeable water system Zinc ion battery according to claim 1, it is characterised in that：The barrier film is with excellent leaching
Fibreglass diaphragm, filter paper or the Teflon septum of lubricant nature.
5. chargeable water system Zinc ion battery according to claim 1, it is characterised in that：The active material of described negative pole
Using metal zinc metal sheet, zinc powder or zinc carbon complex.
6. chargeable water system Zinc ion battery according to claim 1, it is characterised in that：The soluble-salt of described zinc is
Trifluoromethayl sulfonic acid zinc, zinc perchlorate or zinc sulfate.
7. chargeable water system Zinc ion battery according to claim 1, it is characterised in that：Addition in described electrolyte
Agent is the soluble-salt containing vanadium.
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| CN201710369663.4A CN107221716B (en) | 2017-05-23 | 2017-05-23 | Rechargeable aqueous zinc ion battery |
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| CN201710369663.4A CN107221716B (en) | 2017-05-23 | 2017-05-23 | Rechargeable aqueous zinc ion battery |
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| CN107221716B CN107221716B (en) | 2020-08-04 |
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Cited By (21)
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|---|---|---|---|---|
| CN108448168A (en) * | 2018-03-14 | 2018-08-24 | 华中科技大学 | A kind of electrolyte and its preparation method and application for water system zinc ion secondary cell |
| CN108767215A (en) * | 2018-05-15 | 2018-11-06 | 华中科技大学 | A kind of material and the preparation method and application thereof inhibiting zinc dendrite |
| CN108832062A (en) * | 2018-06-13 | 2018-11-16 | 深圳市寒暑科技新能源有限公司 | A kind of Zinc ion battery diaphragm and preparation method thereof |
| CN108878877A (en) * | 2018-07-03 | 2018-11-23 | 中国科学院宁波材料技术与工程研究所 | A kind of water system zinc ion cathode active material for secondary battery and a kind of water system zinc ion secondary cell |
| CN110364771A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | A kind of water system zinc ion soft-package battery and preparation method thereof |
| CN110391415A (en) * | 2018-04-20 | 2019-10-29 | 中国科学院福建物质结构研究所 | A kind of positive electrode active materials and the Zinc ion battery including the positive electrode active materials |
| CN110474044A (en) * | 2019-09-05 | 2019-11-19 | 山东大学 | A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof |
| CN110707268A (en) * | 2019-04-24 | 2020-01-17 | 中南大学 | SiO (silicon dioxide)2-polymer composite water-based battery diaphragm material and preparation method and application thereof |
| CN110727155A (en) * | 2019-11-21 | 2020-01-24 | 烟台大学 | Electrochromic/energy storage dual-function device and application thereof |
| CN111542951A (en) * | 2017-11-17 | 2020-08-14 | 赛伦能源公司 | Secondary electrochemical cell having zinc metal negative electrode and mild aqueous electrolyte and method therefor |
| CN111659407A (en) * | 2020-05-30 | 2020-09-15 | 河南省计量科学研究院 | Zinc ion doped transition metal vanadate nanowire photocatalyst and preparation method thereof |
| CN111900496A (en) * | 2020-06-12 | 2020-11-06 | 北京大学深圳研究生院 | Electrolyte for water-based zinc ion battery and application thereof |
| CN111900497A (en) * | 2020-06-12 | 2020-11-06 | 北京大学深圳研究生院 | Aqueous zinc ion battery electrolyte and application thereof |
| CN111934033A (en) * | 2020-08-20 | 2020-11-13 | 江苏师范大学 | Method for protecting zinc ion battery electrode |
| CN112259729A (en) * | 2020-10-14 | 2021-01-22 | 中国科学院合肥物质科学研究院 | Application of ferroferric oxide as anode material of water-based zinc ion battery |
| CN112614985A (en) * | 2021-01-11 | 2021-04-06 | 江苏师范大学 | Aqueous zinc ion battery and preparation method of positive electrode |
| CN113012948A (en) * | 2021-02-25 | 2021-06-22 | 海南大学 | Preparation method of zinc-carbon composite electrode material for zinc ion energy storage device |
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