CN108574085A - A kind of low temperature Zinc ion battery - Google Patents
A kind of low temperature Zinc ion battery Download PDFInfo
- Publication number
- CN108574085A CN108574085A CN201810240311.3A CN201810240311A CN108574085A CN 108574085 A CN108574085 A CN 108574085A CN 201810240311 A CN201810240311 A CN 201810240311A CN 108574085 A CN108574085 A CN 108574085A
- Authority
- CN
- China
- Prior art keywords
- zinc
- ion battery
- low temperature
- electrolyte
- zinc ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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
Abstract
The invention belongs to battery technology field, specially a kind of low temperature Zinc ion battery.Zinc ion battery of the present invention includes anode, cathode, low-temperature electrolyte, and the positive electrode includes the organic matter containing carbonyl functional group such as quinones, being capable of reversible deintercalation Zn2+、Li+、Na+Inlaid scheme or Prussian blue derivative；The cathode includes metal zinc metal sheet, zinc foil, zinc powder, powder porous zinc electrode, kirsite or applies/be deposited on Zr-based materials in other conductive substrates；The low-temperature electrolyte is using ethyl acetate and its derivative or ketone and its derivative as solvent, using organic zinc salt or inorganic zinc salt as solute, a concentration of 0.01 10 mol/L.The Zinc ion battery of the present invention carries out reversible charge and discharge by the reaction of positive enolization and cathode zinc dissolving/precipitation mechanism, and higher specific capacity and energy density, long circulation life and excellent power-performance are still shown under extremely low temperature (70 DEG C).
Description
Technical field
The invention belongs to battery technology fields, and in particular to a kind of Zinc ion battery.
Background technology
Energy crisis and the major issue of environmental pollution are faced, the effective exploitation and utilization to green clean energy resource become extremely
Close important solution.However, the novel energies such as regenerative resource such as solar energy, wind energy, tide energy have discontinuous spy
Point efficiently uses and needs efficient and recyclable energy storage device, can discontinuous regenerative resource be integrated into power grid
And in energy infrastructure electrification application.The development and application that the energy storage systems such as secondary cell and capacitor can be filled is to realize to be somebody's turn to do
The effective way of target.Current a plurality of types of secondary cells have been developed that, including commercialized lead-acid battery and lithium-ion electric
Pond has been widely used in the fields such as electric vehicle, mobile phone mobile communication, computer.Although lithium ion battery can show height
Energy density, long circulation life, still, high cost and safety problem be still interfere its be applied to extensive energy storage it is important because
Element.The lead-acid battery cost for occupying more than half Battery Market is relatively low, this advantage is conducive to extensive energy storage, but lead itself has
Toxicity can cause environment hidden danger, and energy density and cycle life are extremely limited.Other commercialization secondary cells, such as ni-Cd electricity
Pond, Ni-MH battery, also by environmental pollution, cycle life is poor, of high cost the defects of limited.Therefore, developing low-cost, high energy
Metric density, the energy storage system of long circulation life are highly important research directions.
Current many novel battery systems are reported in succession, further include being based on Na in addition to lithium ion battery+、K+、Mg2+、Zn2 +、Ni2+、Al3+Or the metal ion battery of mixed type.Wherein, with Zn2+As the Zinc ion battery of electric charge transfer active material,
Using metallic zinc resourceful, at low cost, environmental-friendly, with height ratio capacity (820 mAh/g) as negative material, it is subject to
Suitable positive electrode is found, the Zinc ion battery assembled has very vast potential for future development, can be used for large-scale energy storage.
Transition metal oxide and Prussian blue derivative are the Zinc ion battery positive electrodes mainly studied at present at present, they are still deposited
In the defect that cycle life is limited or specific capacity/energy density is low.Therefore, it finds with height ratio capacity, high charge-discharge invertibity
Positive electrode be improve Zinc ion battery performance important directions.Traditional inorganic electrode material is to pass through Zn2+In lattice
Intercalation/deintercalation realize reversible charge and discharge, due to Zn2+It constantly shuttles in lattice, positive electrode is in the charge and discharge process repeated
In be difficult to avoid that can recurring structure change, to cause battery cycle life extremely limited.Organic matter with carbonyl functional group,
Such as quinones, carbonyl and metal ions M (M=Li can be passed through+,Na+Deng) reversible enolization reaction (formation-C-O-M keys) realize
The reversible storage of charge.This entirely different Mechanism of electrochemical behaviors of anhydrous avoids ion intercalation/deintercalation pair in electrode material lattice
The change of electrode material structure to realize that the long circulation life of battery provides the foundation, and has faster kinetics.
Therefore, be using the organic matter that contains carbonyl functional group as electrode active material prepare with long circulation life, high-energy density,
The important research strategy of the Zinc ion battery of excellent power-performance.
In addition, various countries are directed to the development plan of battery all to promote energy density and cycle performance as target at present.From two
Since primary cell is commercialized, as new material, new system continually develop application, it is close that current energy storage system realizes energy
Being obviously improved for the performances such as degree, power density and cycle life, promotes extensive use of the secondary cell in numerous areas.But
It is that at the same time, the problem poor to the adaptability of application environment becomes increasingly conspicuous, and cannot meet people for particular surroundings
The middle demand used.If occupied the lithium ion battery of secondary cell staple market at present, height can express under room temperature although realizing
Energy density, high power density and long circulation life, but the performance under low temperature environment is extremely limited, in the environment less than -30 DEG C
Under almost can not normal use.Therefore, the deficiency of battery cryogenic property becomes one of the main bottleneck of battery Developing Extension, solves
Under battery low temperature the problem of poor performance, improves the cryogenic property of battery and become urgently to be resolved hurrily to expand its use scope and important ask
Topic.
The main reason for battery poor performance at low temperatures, comes from electrolyte fusing point height under low temperature, is solidified under low temperature or half solidifies,
The factors such as ionic conductivity acutely declines, electrode is sharply increased with electrolyte interface impedance and ion diffusion velocity slows down are related.
The external means taken at present for the insufficient defect of battery cryogenic property include mainly battery is heated, to build constant temperature small
Environment etc., although performance of the battery in low temperature environment can be improved to a certain extent, cause use cost increase and
The problem of additional equipment is born.One of most direct and effective method is optimization and improves electrolyte to improve battery low temperature properties
Energy.The ideal electrolyte for low temperature environment should have the characteristics that：High conductivity；High de-agglomeration voltage；High stability has
Wide temperature window；Environmental effect is small；Inertia does not react with electrode material.Developing has height under low melting point, wide temperature window
The electrolyte of conductivity is to improve the effective important method of battery cryogenic property.
Therefore, a kind of Zinc ion battery based on low-temperature electrolyte of exploitation has a very important significance, and can be used as one kind
Low cost, high-energy density, the novel energy-storing system that excellent electrochemical performance is shown in wide temperature range, in large-scale energy storage
Equal fields have very wide foreground.
Invention content
The low cost that the purpose of the present invention is to provide a kind of based on low-temperature electrolyte, long circulation life, high-energy density,
And the Zinc ion battery of low temperature performance excellent.
Zinc ion battery provided by the invention, with the organic matter containing carbonyl functional group such as quinones, being capable of reversible deintercalation Zn2+、
Li+、Na+Inlaid scheme or Prussian blue derivative etc. as a positive electrode active material, using Zr-based materials as negative electrode active
Substance, solution using ethyl acetate or acetone and its derivative as solvent, organic zinc salt and inorganic zinc salt as solute as
Electrolyte；The agent in electrolyte has many advantages, such as to show higher ionic conductivity under lower fusing point, low temperature.
In the present invention, in the low-temperature electrolyte, solute removes cation Zn2+Outside, it can also include Li+、Na+、 K+、 Mg2 +、 Ni2+、 Al3+Further include additive Deng other cations.
In the present invention, when containing the organic matter of carbonyl functional group as positive electrode active materials using quinones etc., Zinc ion battery
Working mechanism is：When battery discharge, the Zn in electrolyte2+It is anti-that reversible enolization is carried out with the carbonyl (- C=O) on positive electrode
It answers, formation-C-O-Zn-O-C- keys, realizes Zn2+Reversible storage；Meanwhile the dissolving of zinc occurring on cathode Zr-based materials, it is formed
Zn2+Into in electrolyte, which flows to anode in external circuit with electronics by cathode；Charging process in contrast, Zn2+
It is come back in electrolyte from positive electrode ,-C-O-Zn-O-C- keys become carbonyl again, while with the Zn in electrolyte2+
It is deposited on cathode, electronics flows to cathode in external circuit by anode.The reversible enol for the positive electrode that the reaction mechanism is related to
Change dissolving/deposition process of zinc on reaction and cathode with kinetics quickly, and the Reversible Cycle of overlength can be carried out
And capacity hardly happens decaying.
Reaction mechanism is as follows：
Anode：2R-C=O+ Zn2++2e-↔R-C-O-Zn-O-C-R；Cathode：Zn↔ Zn2++ 2e-
Wherein, R is organic group, it may include carbonyl group.
In the present invention, the organic matter containing carbonyl functional group includes quinones, such as pyrene -4,5,9,10- tetrones, poly- pyrene -
One or more of 4,5,9,10- tetrones, cup [4]-quinone.
In the present invention, described being capable of reversible deintercalation Zn2+、Li+、Na+Inlaid scheme, including transition metal M1Oxidation
In object, sulfide, phosphide, chloride and metallic element adulterates M2One or more of above-mentioned substance；Wherein, M1=
Ni, Mn, Fe, Co, Ti, V or Mo, M2=Li, Na, Mg, Al, Zn, Cu, Cr, Mn or La.
In the present invention, the Prussian blue derivant structure formula is：AxM[M’(CN)6]y·(H2O)z, A Li, Na, K,
The metals such as Zn, Mg, Ca, Sr, Ba, Cs, Al or Y, M Cu, Zn, Ni, Fe, Co, Mn or V, M ' or Fe, Co, Cr or Ru etc., 0≤
X≤2,0≤y<<1,0≤z≤2-x+6y.
In the present invention, anode can be prepared by spreading as follows：Positive active material is mixed into system with conductive agent, binder
At slurry, coating on a current collector, is cut after vacuum drying, and pole piece is made；Or anode active material slurry is rolled, film is made, very
Compacting, which is cut, after sky drying obtains electrode on a current collector.The collector includes titanium foil, stainless steel foil, aluminium foil, carbon cloth, graphite
One or more of alkene, carbon fiber paper, titanium net, stainless (steel) wire, aluminium net；The conductive agent includes activated carbon, acetylene black, charcoal
The quality of one or more of black, carbon nanotube, carbon fiber, graphene, graphite, mesoporous carbon, conductive agent is no more than cathode film
The 30% of gross mass；The binder includes polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose
(CMC), one or more of water-soluble rubber, polyvinyl alcohol (PVA), binder quality are no more than cathode film gross mass
10%。
In the present invention, the zinc-base negative material includes metal zinc metal sheet, zinc foil, zinc powder, powder porous zinc electrode, zinc conjunction
Gold applies/is deposited on Zinc material etc. in other conductive substrates.
In the present invention, the low-temperature electrolyte is using ethyl acetate or acetone and its derivative as solvent, ethyl acetate
And its derivative, include the one or more of acetyl triethyl, ethyl acetoacetate, gamma-butyrolacton；The acetone and its derivative
Organic solvent, including acetone, butanone, diacetyl, methylisobutylketone, cyclobutanone, pentanone, cyclopentanone, hexanone, cyclohexanone and it
Isomer and one or more of derivative.
In the present invention, the low-temperature electrolyte is using organic zinc salt and inorganic zinc salt as solute, including trifluoromethyl sulphur
Sour zinc, bis- (trifluoromethanesulp-onyl -onyl imide) zinc, three (trimethyl fluoride sulfonyl methyl) ions, zinc perchlorate, zinc sulfate, zinc nitrate,
One or more of tetrafluoro boric acid zinc, zinc chloride, zinc fluoride, zinc bromide, zinc iodide.
In the present invention, zinc salt concentration range is 0.01-10mol/L.
In the present invention, the low-temperature electrolyte is in addition to containing Zn2+It is cationic outer, it also may include Li+, Na+, K+, Mg2+,
Ni2+, Al3+One or more of, anion include trifluoromethane sulfonic acid ion, bis- (trifluoromethanesulp-onyl -onyl imide) ions,
Three (trimethyl fluoride sulfonyl methyl) ions, perchlorate, sulfate radical, nitrate anion, tetrafluoroborate, chlorion, fluorine ion, bromine from
One or more of son, iodide ion.
In the present invention, the additive includes carbonates, borate ester, sulfurous esters, sultones class, fluoro second
One or more of enester, polyoxy ether.
In the present invention, the content of the additive is the 0.1%-10% of electrolyte weight score.
Zinc ion battery in the present invention carries out reversible fill by the reaction of positive enolization and cathode zinc dissolving/precipitation mechanism
Electric discharge, still shows higher specific capacity and energy density, long circulation life and excellent power under extremely low temperature (- 70 DEG C)
Performance.
Specific implementation mode
Further to clearly demonstrate technical scheme of the present invention and advantage, the present invention is said with following specific examples
It is bright, but the invention is not limited in these examples.
Embodiment 1
Under the conditions of anhydrous and oxygen-free, using ethyl acetate as solvent, trifluoromethane sulfonic acid zinc is dissolved according to the concentration of 2 mol/L
In ethyl acetate, the low-temperature electrolyte is obtained.With pyrene -4,5,9,10- tetrones (PTO) as a positive electrode active material, with conductive agent
Carbon black and polyfluortetraethylene of binding element (PTFE) are according to mass ratio 6:3:1 ratio is mixed and made into slurry, rolls and is dried after film is made,
It is compressed on after cutting in titanium net and anode pole piece is made.Using metal zinc metal sheet as cathode, it is assembled into zinc ion button cell.It assembles
Zinc ion battery charge-discharge test is carried out with 0.1C multiplying powers on electrochemical workstation, specific capacity is 352 at 25 DEG C of room temperature
mAh g-1(be based on positive active material Mass Calculation), specific capacity is 248 mAh g at -40 DEG C of low temperature-1, -70 DEG C of ultralow temperature
Shi Rongliang still reaches 170 mAh g-1。
Embodiment 2
Under the conditions of anhydrous and oxygen-free, using ethyl acetate as solvent, trifluoromethane sulfonic acid zinc is dissolved according to the concentration of 2 mol/L
In ethyl acetate, the low-temperature electrolyte is obtained.With poly- pyrene -4,5,9,10- tetrones (PPTO) as a positive electrode active material, with conduction
Agent activated carbon and binder Kynoar (PVDF) are according to mass ratio 6:3:1 ratio is mixed and made into slurry, rolls after film is made
Drying is compressed in titanium net after cutting and anode pole piece is made.Using metallic zinc foil as cathode, it is assembled into zinc ion button cell.
Assembled Zinc ion battery carries out charge-discharge test on electrochemical workstation with 0.1C multiplying powers, and specific capacity is at 25 DEG C of room temperature
190 mAh g-1(be based on positive active material Mass Calculation), specific capacity is 128 mAh g at -40 DEG C of low temperature-1, ultralow temperature-
Capacity still reaches 103 mAh g at 70 DEG C-1。
Embodiment 3
Under the conditions of anhydrous and oxygen-free, using ethyl acetate as solvent, by zinc sulfate (ZnSO4) be dissolved according to the concentration of 2 mol/L
In ethyl acetate, the low-temperature electrolyte is obtained.As a positive electrode active material with cup [4]-quinone (CAQ), with conductive agent acetylene black and
Binder carboxymethyl cellulose (CMC) is according to mass ratio 6:3:1 ratio is mixed and made into slurry, rolls and is dried after film is made, is cut
After be compressed in titanium net be made anode pole piece.To be deposited on the Zinc material on graphene-based bottom as cathode, it is assembled into zinc ion
Button cell.Assembled Zinc ion battery carries out charge-discharge test, 25 DEG C of room temperature on electrochemical workstation with 0.1C multiplying powers
Lower specific capacity is 305 mAh g-1(be based on positive active material Mass Calculation), specific capacity is 210 mAh g at -40 DEG C of low temperature-1, capacity still reaches 135 mAh g when -70 DEG C of ultralow temperature-1。
Embodiment 4
Under the conditions of anhydrous and oxygen-free, using acetone as solvent, trifluoromethane sulfonic acid zinc is dissolved in acetone according to the concentration of 2 mol/L
In, obtain the low-temperature electrolyte.As a positive electrode active material with Prussian blue derivative (CuHCF), with conductive agent carbon nanotube
With polyfluortetraethylene of binding element (PTFE) according to mass ratio 6:3:1 ratio is mixed and made into slurry, rolls and is dried after film is made, is cut
After be compressed in titanium net be made anode pole piece.Using zinc foil as cathode, it is assembled into zinc ion button cell.Assembled zinc ion
Battery carries out charge-discharge test on electrochemical workstation with 0.1C multiplying powers, and specific capacity is 52 mAh g at 25 DEG C of room temperature-1(base
In positive active material Mass Calculation), specific capacity is 34 mAh g at -40 DEG C of low temperature-1, capacity still reaches when -70 DEG C of ultralow temperature
23 mAh g-1。
Embodiment 5
Under the conditions of anhydrous and oxygen-free, using acetone as solvent, will be bis- (trifluoromethanesulp-onyl -onyl imide) zinc it is molten according to the concentration of 2 mol/L
Solution in acetone, obtains low-temperature electrolyte.With α-MnO2As a positive electrode active material, with conductive agent ordered mesopore carbon (CMK-3)
With binder Kynoar (PVDF) according to mass ratio 6:3:1 ratio is mixed and made into slurry, rolls and is dried after film is made, is cut
After be compressed in titanium net be made anode pole piece.Using zinc foil as cathode, it is assembled into zinc ion button cell.Assembled zinc ion
Battery carries out charge-discharge test on electrochemical workstation with 0.1C multiplying powers, and specific capacity is 220 mAh g at 25 DEG C of room temperature-1 (base
In positive active material Mass Calculation), specific capacity is 151 mAh g at -40 DEG C of low temperature-1, capacity still reaches when -70 DEG C of ultralow temperature
100 mAh g-1。
Embodiment 6
Under the conditions of anhydrous and oxygen-free, using diacetyl as solvent, trifluoromethane sulfonic acid zinc is dissolved in fourth according to the concentration of 2 mol/L
In diketone, the low-temperature electrolyte is obtained.With vanadium phosphate sodium (Na3V2(PO4)3) as a positive electrode active material, with conductive agent graphite and
Polyfluortetraethylene of binding element (PTFE) is according to mass ratio 6:3:1 ratio is mixed and made into slurry, rolls and is dried after film is made, after cutting
It is compressed on stainless (steel) wire and anode pole piece is made.Using zinc foil as cathode, it is assembled into zinc ion button cell.Assembled zinc from
Sub- battery carries out charge-discharge test on electrochemical workstation with 0.1C multiplying powers, and specific capacity is 98 mAh g at 25 DEG C of room temperature-1
(be based on positive active material Mass Calculation), specific capacity is 65 mAh g at -40 DEG C of low temperature-1, capacity still reaches when -70 DEG C of ultralow temperature
To 42 mAh g-1。
Embodiment 7
Under the conditions of anhydrous and oxygen-free, using acetone as solvent, trifluoromethane sulfonic acid zinc is dissolved in acetone according to the concentration of 2 mol/L
In, obtain the low-temperature electrolyte.With Mo6S8As a positive electrode active material, with conductive agent carbon fiber and polyfluortetraethylene of binding element
(PTFE) according to mass ratio 6:3:1 ratio is mixed and made into slurry, rolls and is dried after film is made, and is compressed in aluminium net and is made after cutting
Anode pole piece.Using powder porous zinc electrode as cathode, it is assembled into zinc ion button cell.Assembled Zinc ion battery is in electricity
Charge-discharge test is carried out with 0.1C multiplying powers on chem workstation, specific capacity is 90 mAh g at 25 DEG C of room temperature-1It is (living based on anode
Property material mass calculate), specific capacity is 61 mAh g at -40 DEG C of low temperature-1, capacity still reaches 41 mAh g when -70 DEG C of ultralow temperature-1。
Embodiment 8
Under the conditions of anhydrous and oxygen-free, using ethyl acetate as solvent, by zinc nitrate (ZnNO3) be dissolved according to the concentration of 1 mol/L
In ethyl acetate, the low-temperature electrolyte is obtained.With LiMn2O4 (LiMn2O4) as a positive electrode active material, with conductive agent carbon fiber and
Polyfluortetraethylene of binding element (PTFE) is according to mass ratio 6:3:1 ratio is mixed and made into slurry, rolls and is dried after film is made, after cutting
It is compressed in aluminium net and anode pole piece is made.Using zinc foil as cathode, it is assembled into zinc ion button cell.Assembled zinc ion electricity
Pond carries out charge-discharge test on electrochemical workstation with 0.1C multiplying powers, and specific capacity is 108 mAh g at 25 DEG C of room temperature-1It (is based on
Positive active material Mass Calculation), specific capacity is 75 mAh g at -40 DEG C of low temperature-1, capacity reaches 45 when -70 DEG C of ultralow temperature
mAh g-1。
Table 1 is compared using the performance of Different electrodes material and the low temperature Zinc ion battery of electrolyte
。
Claims (10)
1. a kind of low temperature Zinc ion battery, which is characterized in that with organic matter of the quinones containing carbonyl functional group, being capable of reversible deintercalation Zn2 +、Li+、Na+Inlaid scheme or Prussian blue derivative as a positive electrode active material, using Zr-based materials as negative electrode active
Substance, solution using ethyl acetate or acetone and its derivative as solvent, organic zinc salt or inorganic zinc salt as solute as
Electrolyte.
2. low temperature Zinc ion battery according to claim 1, which is characterized in that in the electrolyte, remove cation Zn2+
Outside, also other cations Li+、Na+、 K+、 Mg2+、 Ni2+、 Al3+One or more of；It further include additive.
3. low temperature Zinc ion battery according to claim 1 or 2, which is characterized in that the function containing carbonyl such as described quinones
The organic matter of group is selected from one or more of pyrene -4,5,9,10- tetrones, poly- pyrene -4,5,9,10- tetrones, cup [4]-quinone；It is described
Being capable of reversible deintercalation Zn2+、Li+、Na+Inlaid scheme be selected from transition metal M1Oxide, sulfide, phosphide, chlorination
Object and doped metallic elements M2One or more of above-mentioned substance；Wherein, M1For Ni, Mn, Fe, Co, Ti, V or Mo, M2
For Li, Na, Mg, Al, Zn, Cu, Cr, Mn or La；The Prussian blue derivant structure formula is AxM[M’(CN)6]y·
(H2O)z, wherein A is Li, Na, K, Zn, Mg, Ca, Sr, Ba, Cs, Al or Y, and M Cu, Zn, Ni, Fe, Co, Mn or V, M ' is
Fe, Co, Cr or Ru, 0≤x≤2,0≤y<<1,0≤z≤2-x+6y.
4. low temperature Zinc ion battery according to claim 3, which is characterized in that the Zr-based materials be metal zinc metal sheet,
Zinc foil, zinc powder, powder porous zinc electrode or kirsite, or apply/be deposited on the Zinc material in other conductive substrates.
5. low temperature Zinc ion battery according to claim 1,2 or 4, which is characterized in that the ethyl acetate and its spread out
Biology is the one or more of acetyl triethyl, ethyl acetoacetate, gamma-butyrolacton；The ketone and its derivative are organic molten
Agent is acetone, butanone, diacetyl, methylisobutylketone, cyclobutanone, pentanone, cyclopentanone, hexanone, cyclohexanone and their same point
One or more of isomers and derivative.
6. low temperature Zinc ion battery according to claim 5, which is characterized in that the zinc solute include organic zinc salt and
Inorganic zinc salt, selected from trifluoromethane sulfonic acid zinc, bis- (trifluoromethanesulp-onyl -onyl imide) zinc, three (trimethyl fluoride sulfonyl methyl) zinc, height
One or more of zinc chlorate, zinc sulfate, zinc nitrate, tetrafluoro boric acid zinc, zinc chloride, zinc fluoride, zinc bromide, zinc iodide.
7. according to the low temperature Zinc ion battery described in claim 1,2,4 or 6, which is characterized in that in the low-temperature electrolyte,
The concentration range of contained zinc ion is 0.01 ~ 10 mol/L.
8. low temperature Zinc ion battery according to claim 7, which is characterized in that in the low-temperature electrolyte, anion
For trimethyl fluoride sulfonyl ion, bis- (trifluoromethanesulp-onyl -onyl imide) ions, three (trimethyl fluoride sulfonyl methyl) ions, sulfate radical,
One or more of nitrate anion, tetrafluoroborate, chlorion, fluorine ion, bromide ion, iodide ion.
9. according to the low temperature Zinc ion battery described in claim 1,2,4,6 or 8, which is characterized in that in the low-temperature electrolyte,
Additive be carbonates, borate ester, sulfurous esters, sultones class, fluorinated ethylene ester, one kind in polyoxy ether or
It is several.
10. low temperature Zinc ion battery according to claim 9, which is characterized in that the content of the additive is electrolyte
The 0.1%-10% of weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810240311.3A CN108574085A (en) | 2018-03-22 | 2018-03-22 | A kind of low temperature Zinc ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810240311.3A CN108574085A (en) | 2018-03-22 | 2018-03-22 | A kind of low temperature Zinc ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108574085A true CN108574085A (en) | 2018-09-25 |
Family
ID=63574580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810240311.3A Pending CN108574085A (en) | 2018-03-22 | 2018-03-22 | A kind of low temperature Zinc ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108574085A (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109994785A (en) * | 2018-12-30 | 2019-07-09 | 华中科技大学 | A kind of zinc organic battery and application |
| CN110444822A (en) * | 2019-08-15 | 2019-11-12 | 哈尔滨工业大学 | A kind of preparation method of the quasi- solid-state Zinc ion battery of integration |
| CN110482516A (en) * | 2019-08-06 | 2019-11-22 | 河北大学 | A kind of anode for zinc-base battery can be filled and zinc-base battery can be filled |
| CN110534808A (en) * | 2019-08-06 | 2019-12-03 | 河北大学 | A kind of fire-retardant organic electrolyte for zinc battery can be filled and zinc battery can be filled |
| CN110727155A (en) * | 2019-11-21 | 2020-01-24 | 烟台大学 | Electrochromic/energy storage dual-function device and application thereof |
| CN110994045A (en) * | 2019-11-20 | 2020-04-10 | 瑞海泊(青岛)能源科技有限公司 | Zinc ion battery and manufacturing method thereof |
| CN111416129A (en) * | 2019-01-04 | 2020-07-14 | 中国科学院福建物质结构研究所 | Acid-base asymmetric electrolyte zinc-quinone battery |
| CN111509306A (en) * | 2020-04-26 | 2020-08-07 | 河北大学 | Electrolyte for rechargeable zinc ion battery, preparation method of electrolyte and rechargeable zinc ion battery |
| CN111600081A (en) * | 2020-06-02 | 2020-08-28 | 南开大学 | Rechargeable water-based zinc ion battery with wide temperature range and long cycle life |
| CN111916709A (en) * | 2020-08-13 | 2020-11-10 | 电子科技大学 | Preparation method of electrode material for water system zinc ion hybrid energy storage device |
| CN111916720A (en) * | 2020-07-30 | 2020-11-10 | 山东大学 | Alloy type negative electrode material of water system rechargeable zinc ion battery and preparation method and application thereof |
| KR20210060910A (en) * | 2019-11-19 | 2021-05-27 | 순천향대학교 산학협력단 | Zinc-ion secondary battery comprising Prussian Blue Analogous(PBAs) cathode |
| CN113140807A (en) * | 2021-04-21 | 2021-07-20 | 浙江大学 | Water battery with incombustibility |
| CN113782710A (en) * | 2021-09-17 | 2021-12-10 | 中国计量大学 | High-performance chargeable and dischargeable aqueous zinc-iodine battery and preparation method thereof |
| US20220006088A1 (en) * | 2020-07-03 | 2022-01-06 | Huazhong University Of Science And Technology | Zinc organic battery and application thereof |
| CN113921900A (en) * | 2021-09-24 | 2022-01-11 | 天津大学 | Zinc-based electrochemical energy storage device |
| CN114094208A (en) * | 2021-10-13 | 2022-02-25 | 瑞海泊有限公司 | Electrolyte for aqueous zinc ion battery and aqueous zinc ion battery |
| CN114388901A (en) * | 2021-12-06 | 2022-04-22 | 华中科技大学 | Aqueous zinc ion battery electrolyte and battery |
| CN114628801A (en) * | 2022-03-21 | 2022-06-14 | 中国科学院化学研究所 | Aqueous electrolyte based on deuterated water, preparation method thereof and application of aqueous electrolyte in metal ion secondary battery |
| CN114695975A (en) * | 2022-03-21 | 2022-07-01 | 电子科技大学 | Preparation method of low-temperature flexible zinc ion battery |
| CN114695973A (en) * | 2022-03-21 | 2022-07-01 | 电子科技大学 | Preparation method of low-temperature zinc ion battery |
| CN114865110A (en) * | 2022-05-10 | 2022-08-05 | 吉林大学 | Mixed water-based zinc ion battery electrolyte with stable pH value and application thereof |
| CN117613432A (en) * | 2024-01-24 | 2024-02-27 | 中南大学 | Containing acyl esters C having both keto and ester groups 5~8 Aqueous zinc ion battery composite electrolyte of alkane chain-like organic additive, and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60258861A (en) * | 1984-06-06 | 1985-12-20 | Toshiba Battery Co Ltd | Manufacture of alkaline battery |
| CN103378370A (en) * | 2012-04-24 | 2013-10-30 | 张家港市国泰华荣化工新材料有限公司 | Lithium iodide organic electrolyte for lithium iron battery and preparation method thereof |
| CN103915647A (en) * | 2014-03-31 | 2014-07-09 | 上虞安卡拖车配件有限公司 | Low-temperature lithium ion battery |
| CN104885286A (en) * | 2012-12-20 | 2015-09-02 | 索尔维公司 | Salts of N-containing heterocyclic anions as components in electrolytes |
| CN106169611A (en) * | 2016-09-17 | 2016-11-30 | 复旦大学 | A kind of low-temperature electrolyte with ethyl acetate as solvent |
| CN106374141A (en) * | 2016-09-04 | 2017-02-01 | 复旦大学 | Keto-solvent-based low-temperature electrolyte |
| CN107565134A (en) * | 2017-07-22 | 2018-01-09 | 复旦大学 | Water system Zinc ion battery based on the tetrone positive pole of pyrene 4,5,9,10 and zinc load |
-
2018
- 2018-03-22 CN CN201810240311.3A patent/CN108574085A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60258861A (en) * | 1984-06-06 | 1985-12-20 | Toshiba Battery Co Ltd | Manufacture of alkaline battery |
| CN103378370A (en) * | 2012-04-24 | 2013-10-30 | 张家港市国泰华荣化工新材料有限公司 | Lithium iodide organic electrolyte for lithium iron battery and preparation method thereof |
| CN104885286A (en) * | 2012-12-20 | 2015-09-02 | 索尔维公司 | Salts of N-containing heterocyclic anions as components in electrolytes |
| CN103915647A (en) * | 2014-03-31 | 2014-07-09 | 上虞安卡拖车配件有限公司 | Low-temperature lithium ion battery |
| CN106374141A (en) * | 2016-09-04 | 2017-02-01 | 复旦大学 | Keto-solvent-based low-temperature electrolyte |
| CN106169611A (en) * | 2016-09-17 | 2016-11-30 | 复旦大学 | A kind of low-temperature electrolyte with ethyl acetate as solvent |
| CN107565134A (en) * | 2017-07-22 | 2018-01-09 | 复旦大学 | Water system Zinc ion battery based on the tetrone positive pole of pyrene 4,5,9,10 and zinc load |
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109994785A (en) * | 2018-12-30 | 2019-07-09 | 华中科技大学 | A kind of zinc organic battery and application |
| CN111416129A (en) * | 2019-01-04 | 2020-07-14 | 中国科学院福建物质结构研究所 | Acid-base asymmetric electrolyte zinc-quinone battery |
| CN111416129B (en) * | 2019-01-04 | 2021-07-20 | 中国科学院福建物质结构研究所 | Acid-base asymmetric electrolyte zinc-quinone battery |
| CN110482516B (en) * | 2019-08-06 | 2021-05-28 | 河北大学 | Positive electrode for rechargeable zinc-based battery and rechargeable zinc-based battery |
| CN110482516A (en) * | 2019-08-06 | 2019-11-22 | 河北大学 | A kind of anode for zinc-base battery can be filled and zinc-base battery can be filled |
| CN110534808A (en) * | 2019-08-06 | 2019-12-03 | 河北大学 | A kind of fire-retardant organic electrolyte for zinc battery can be filled and zinc battery can be filled |
| CN110534808B (en) * | 2019-08-06 | 2021-07-30 | 河北大学 | Flame-retardant organic electrolyte for rechargeable zinc battery and rechargeable zinc battery |
| CN110444822A (en) * | 2019-08-15 | 2019-11-12 | 哈尔滨工业大学 | A kind of preparation method of the quasi- solid-state Zinc ion battery of integration |
| KR102406480B1 (en) * | 2019-11-19 | 2022-06-08 | 순천향대학교 산학협력단 | Zinc-ion secondary battery comprising Prussian Blue Analogous(PBAs) cathode |
| KR20210060910A (en) * | 2019-11-19 | 2021-05-27 | 순천향대학교 산학협력단 | Zinc-ion secondary battery comprising Prussian Blue Analogous(PBAs) cathode |
| CN110994045A (en) * | 2019-11-20 | 2020-04-10 | 瑞海泊(青岛)能源科技有限公司 | Zinc ion battery and manufacturing method thereof |
| CN110994045B (en) * | 2019-11-20 | 2022-02-08 | 瑞海泊(青岛)能源科技有限公司 | Zinc ion battery and manufacturing method thereof |
| CN110727155A (en) * | 2019-11-21 | 2020-01-24 | 烟台大学 | Electrochromic/energy storage dual-function device and application thereof |
| CN110727155B (en) * | 2019-11-21 | 2021-11-30 | 烟台大学 | Electrochromic/energy storage dual-function device and application thereof |
| CN111509306A (en) * | 2020-04-26 | 2020-08-07 | 河北大学 | Electrolyte for rechargeable zinc ion battery, preparation method of electrolyte and rechargeable zinc ion battery |
| CN111509306B (en) * | 2020-04-26 | 2021-06-25 | 河北大学 | Electrolyte for rechargeable zinc ion battery, preparation method of electrolyte and rechargeable zinc ion battery |
| CN111600081A (en) * | 2020-06-02 | 2020-08-28 | 南开大学 | Rechargeable water-based zinc ion battery with wide temperature range and long cycle life |
| US20220006088A1 (en) * | 2020-07-03 | 2022-01-06 | Huazhong University Of Science And Technology | Zinc organic battery and application thereof |
| US11522192B2 (en) * | 2020-07-03 | 2022-12-06 | Huazhong University Of Science And Technology | Zinc organic battery and application thereof |
| CN111916720A (en) * | 2020-07-30 | 2020-11-10 | 山东大学 | Alloy type negative electrode material of water system rechargeable zinc ion battery and preparation method and application thereof |
| CN111916709A (en) * | 2020-08-13 | 2020-11-10 | 电子科技大学 | Preparation method of electrode material for water system zinc ion hybrid energy storage device |
| CN113140807A (en) * | 2021-04-21 | 2021-07-20 | 浙江大学 | Water battery with incombustibility |
| CN113782710A (en) * | 2021-09-17 | 2021-12-10 | 中国计量大学 | High-performance chargeable and dischargeable aqueous zinc-iodine battery and preparation method thereof |
| WO2023044969A1 (en) * | 2021-09-24 | 2023-03-30 | 天津大学 | Zinc-based electrochemical energy storage device |
| CN113921900A (en) * | 2021-09-24 | 2022-01-11 | 天津大学 | Zinc-based electrochemical energy storage device |
| CN113921900B (en) * | 2021-09-24 | 2024-04-12 | 天津大学 | Zinc-based electrochemical energy storage device |
| CN114094208A (en) * | 2021-10-13 | 2022-02-25 | 瑞海泊有限公司 | Electrolyte for aqueous zinc ion battery and aqueous zinc ion battery |
| CN114388901A (en) * | 2021-12-06 | 2022-04-22 | 华中科技大学 | Aqueous zinc ion battery electrolyte and battery |
| CN114628801A (en) * | 2022-03-21 | 2022-06-14 | 中国科学院化学研究所 | Aqueous electrolyte based on deuterated water, preparation method thereof and application of aqueous electrolyte in metal ion secondary battery |
| CN114695975A (en) * | 2022-03-21 | 2022-07-01 | 电子科技大学 | Preparation method of low-temperature flexible zinc ion battery |
| CN114695973A (en) * | 2022-03-21 | 2022-07-01 | 电子科技大学 | Preparation method of low-temperature zinc ion battery |
| CN114865110A (en) * | 2022-05-10 | 2022-08-05 | 吉林大学 | Mixed water-based zinc ion battery electrolyte with stable pH value and application thereof |
| CN114865110B (en) * | 2022-05-10 | 2024-04-12 | 吉林大学 | Mixed water system zinc ion battery electrolyte with stable pH value and application |
| CN117613432A (en) * | 2024-01-24 | 2024-02-27 | 中南大学 | Containing acyl esters C having both keto and ester groups 5~8 Aqueous zinc ion battery composite electrolyte of alkane chain-like organic additive, and preparation method and application thereof |
| CN117613432B (en) * | 2024-01-24 | 2024-04-09 | 中南大学 | Aqueous zinc ion battery composite electrolyte and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108574085A (en) | A kind of low temperature Zinc ion battery | |
| Olbasa et al. | High-rate and long-cycle stability with a dendrite-free zinc anode in an aqueous Zn-ion battery using concentrated electrolytes | |
| CN105449186B (en) | A kind of secondary cell and preparation method thereof | |
| CN105789690B (en) | Rechargeable magnesium battery and preparation method thereof | |
| CN102945947B (en) | Preparation method of flexible binding agent-free self-support combination electrode | |
| CN107785603B (en) | Lithium-sulfur cell electrolyte and preparation method thereof and the battery for using the electrolyte | |
| CN102820454B (en) | Electrode composite material and preparation method thereof, positive pole, there is this anodal battery | |
| US20140349177A1 (en) | Magnesium hybrid battery and its fabrication method | |
| CN106784629A (en) | A kind of lithium metal battery cathode interface method of modifying | |
| Chen et al. | Perchlorate based “oversaturated gel electrolyte” for an aqueous rechargeable hybrid Zn–Li battery | |
| CN107346834A (en) | Without lithium salts addition composite solid electrolyte material, dielectric film and preparation method thereof | |
| CN113140723A (en) | Wide-temperature-range sodium ion battery based on metal bismuth cathode | |
| CN103579590A (en) | Preparation method for coating anode material of lithium battery | |
| CN106602129B (en) | A kind of polyion battery and preparation method thereof | |
| CN108242560A (en) | Zinc-base Dual-ion cell and preparation method thereof | |
| CN105514378A (en) | Lithium-sulfur battery positive-pole composite material with imitated cellular structure and preparation method thereof | |
| CN103367791B (en) | A kind of new type lithium ion battery | |
| CN102916195A (en) | Graphene-coated copper oxide composite cathode material and method for manufacturing same | |
| CN106374141A (en) | Keto-solvent-based low-temperature electrolyte | |
| CN109904441A (en) | A kind of lithium ion battery negative material, lithium ion battery with nonaqueous electrolyte and preparation method thereof | |
| CN111952670A (en) | Lithium ion battery with wide working temperature range | |
| CN102097653B (en) | Electrolyte used for Li-S battery, Li-S battery and method for preparing electrolyte membrane contained in same | |
| CN108172406A (en) | One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material | |
| CN113937336A (en) | Wide-temperature mixed ion battery based on lithium iron phosphate anode and tin-carbon cathode | |
| Xiao et al. | Zn-based batteries for energy storage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180925 |
|
| WD01 | Invention patent application deemed withdrawn after publication |