CN110010982A - Battery - Google Patents
Battery Download PDFInfo
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- CN110010982A CN110010982A CN201810012406.XA CN201810012406A CN110010982A CN 110010982 A CN110010982 A CN 110010982A CN 201810012406 A CN201810012406 A CN 201810012406A CN 110010982 A CN110010982 A CN 110010982A
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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
-
- 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
-
- 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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- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of battery, adds polyethylene glycol in the electrolyte of the battery.Battery of the invention increases the corrosion resistance of electrode, improves the performance of battery, especially battery capacity and circulation ability.It is not only safe and reliable and have a longer life expectancy, and very convenient carrying and storage, in fields such as the portable electronic products such as such as mobile phone, laptop, electric car, electric bicycle, electric tools with considerable application prospect.
Description
Technical field
The invention belongs to electrochemical energy storage fields, and in particular to a kind of battery, especially a kind of rechargeable water system are mixed
It closes battery (ReHAB).
Background technique
The mankind result in the rapidly expansion in secondary cell market to the extensive utilization of new energy.In current new energy system
Requirement to secondary cell is ubiquitous.Either electric car, wind energy, solar grid-connected or peak load regulation network are all badly in need of one
The secondary cell that kind is cheap, reliable, safety and service life are long.The secondary cell developed at present be concentrated mainly on lithium ion battery,
The high temperature sodium-sulphur battery, sodium nickel chlorine battery and vanadium flow battery.These batteries all have the advantages that it is respective, such as lithium ion battery and
The high temperature sodium-sulphur battery service life is long and energy density is high, and vanadium flow battery even more theoretically has the unlimited service life etc..But no matter
Which kind of battery can not all meet the requirement of cheap, reliable, safety and service life length simultaneously.Traditional lithium ion battery is prohibitively expensive,
And there is security risk；The high temperature sodium-sulphur battery manufacturing technology threshold is high, and price is expensive；The multinomial technical bottleneck of vanadium flow battery is at present all
Fail to obtain breakthrough etc..
Many researchers are devoted to the research of aquo-lithium ion battery thus, it is desirable to lithium ion battery be greatly reduced with this
Cost, and propose some with LiMn2O4For anode, the oxide of vanadium such as LiV3O8Deng the electricity for for cathode, water being electrolyte
Pond, but such battery is easy leakage, it is not safe enough, while the capacity of battery is also reduced, so that the service life is shorter.In addition,
Also be inconvenient to carry and store.
Summary of the invention
Problems to be solved by the invention
The present invention is intended to provide one kind is safe and reliable, lasts a long time, and the battery that performance is greatly improved, especially a kind of tool
There is the rechargeable water system hybrid battery (ReHAB) of above-mentioned excellent properties.
The solution to the problem
The application provides a kind of battery, including anode, cathode and electrolyte, and the electrolyte includes electrolyte and can be molten
At least one of aqueous solution or the alcoholic solution for solving the electrolyte and making the electrolyte ionization；Wherein: the electrolyte
It further include polyethylene glycol.
According to battery described herein, in which: the additive amount of the volume based on the electrolyte, the polyethylene glycol is
0.1~2 volume %.
According to battery described herein, in which: the additive amount of the volume based on the electrolyte, the polyethylene glycol is
1~2 volume %.
According to battery described herein, in which: the additive amount of the volume based on the electrolyte, the polyethylene glycol is
1 volume %.
According to battery described herein, in which: the polyethylene glycol is selected from polyethylene glycol 200, Liquid Macrogol and gathers
At least one of ethylene glycol 400.
According to battery described herein, in which: the volume based on the electrolyte, the electrolyte include: 1 volume %
Polyethylene glycol 200,2 volume % polyethylene glycol 200s, 1 volume % Liquid Macrogol or 1 volume % polyethylene glycol 400.
According to battery described herein, in which: the electrolyte further comprises fumed silica.
According to battery described herein, in which: the additive amount of the weight based on the electrolyte, the polyethylene glycol is
1~2 weight %, the additive amount of the fumed silica are 3~4 weight %.
According to battery described herein, in which: the weight based on the electrolyte, the electrolyte include: 1 weight %
Polyethylene glycol 200 and 4 weight % fumed silicas, 2 weight % polyethylene glycol 200s and 3 weight % fumed silicas, 1 weight
Measure % Liquid Macrogol and 4 weight % fumed silicas, 2 weight % Liquid Macrogols and 3 weight % fumed silicas,
1 weight % polyethylene glycol 400 and 4 weight % fumed silicas or 2 weight % polyethylene glycol 400s and 3 weight % gas phases two
Silica.
According to battery described herein, in which: the partial size of the fumed silica is 20nm or less.
According to battery described herein, the anode includes plus plate current-collecting body and the positive-active for participating in electrochemical reaction
Substance, the positive active material can it is reversible deviate from-embedded ion；The cathode includes at least negative current collector；The electricity
Solution matter can ionize out at least one charge and discharge process the cathode occur reduction-deposition and oxidation-dissolution activity from
Son, the active ion include metal ion, and the metal is selected from least one of Zn, Fe, Cr, Cu, Mn, Ni, Sn.
According to battery described herein, in which: the metal ion is with sulfate, acetate or sulfate and acetate
The form of mixture be present in the electrolyte.
According to battery described herein, in which: the positive active material can it is reversible deviate from-be embedded in lithium ion, sodium
Ion, zinc ion or magnesium ion.
The effect of invention
By inhibiting corrosion and tree, polyethylene glycol and fumed silica significantly to prolong by the anodic protection improved
The available work service life of ReHAB system is grown.For for longer periods saving anode chemical composition, crystalline texture and form, this
Performances are critical a bit, thus for longer periods keep excellent battery performance.
By minimizing the growth of tree, these additives have been also prevented from battery a possibility that short-circuit.For protecting
For holding the performance and stability of battery and improving safety by prevention thermal energy buildup as caused by short circuit, this is necessary
's.
Battery provided by the invention increases the corrosion resistance of electrode, improves the performance of battery, especially battery capacity
And circulation ability.It is not only safe and reliable and have a longer life expectancy, and very convenient carrying and storage, in such as mobile phone, take down notes
The fields such as the portable electronic products such as this computer, electric car, electric bicycle, electric tool have considerable application prospect.
Detailed description of the invention
Fig. 1 is the linear polarisation curves observed when Zn electrode is contacted with different electrolytes.
Fig. 2 is the long-time chronoamperometry experiment curv of zinc foil in different PEG additives in reference electrolyte 1.
Fig. 3 is the chrono-amperometric of zinc foil under different PEG200 concentration under -135mV overvoltage in reference electrolyte 1
The initial stage curve of method measurement.
Fig. 4 be in 3- electrode Swagelok device reference electrolyte 1 and comprising 1%PEG200 reference electrolysis
The CV curve graph of ReHAB battery in liquid 1.
Fig. 5 is the CV curve graph of the ReHAB battery in reference electrolyte 1 in conventional 2- electrode Swagelok battery.
Fig. 6 be in conventional 2- electrode Swagelok battery in the reference electrolyte 1 comprising 1%PEG200 ReHAB
The CV curve graph of battery.
Fig. 7 be reference electrolyte 1 include various concentration PEG200 in the case where ReHAB battery under different multiplying
The figure of discharge capacity.
Fig. 8 is ReHAB battery in the reference electrolyte 1 of the PEG200 in reference electrolyte 1 and comprising different molecular weight
The figure of discharge capacity under different multiplying.
Fig. 9 is to be surveyed using the ReHAB battery of the reference electrolyte 1 of the PEG comprising various concentration at 24 hours and 72 hours
Try the floating charge Capacity Plan under the time.
Figure 10 is the ReHAB battery using the reference electrolyte 1 of the PEG comprising various concentration 24 hours and 72 hours
Floating charge capacity under testing time is than figure.
Figure 11 is the open-circuit voltage figure using the ReHAB battery of the reference electrolyte 1 of the PEG comprising various concentration.
Figure 12 is the discharge capacity using the ReHAB battery of the reference electrolyte 1 of the PEG comprising various concentration at 1C
Figure.
Figure 13 is the discharge capacity using the ReHAB battery of the reference electrolyte 1 comprising different molecular weight PEG at 1C
Figure.
Figure 14 is the discharge capacity figure using the big ReHAB battery of the reference electrolyte 1 comprising PEG at 1C.
Figure 15 is at -135mV using chronoamperometry (CA) discharge capacity figure of the button cell at 4C after 3 hours.
Figure 16 is linear polarisation curves when Zn electrode is contacted from different gel electrolytes.
Figure 17 is the current density obtained afterwards when Zn electrode is contacted from different gel electrolytes using chronoamperometry (CA)
Figure.
Figure 18 be reference example 1 battery using chronoamperometry (CA) afterwards electrode SEM figure.
Figure 19 be comparative example 1 battery using chronoamperometry (CA) afterwards electrode SEM figure.
Figure 20 be embodiment 7 battery using chronoamperometry (CA) afterwards electrode SEM figure.
Figure 21 be embodiment 8 battery using chronoamperometry (CA) afterwards electrode SEM figure.
Figure 22 be embodiment 9 battery using chronoamperometry (CA) afterwards electrode SEM figure.
Figure 23 be embodiment 10 battery using chronoamperometry (CA) afterwards electrode SEM figure.
Figure 24 be embodiment 11 battery using chronoamperometry (CA) afterwards electrode SEM figure.
Figure 25 be embodiment 12 battery using chronoamperometry (CA) afterwards electrode SEM figure.
Figure 26 is the discharge capacity figure of the battery comprising different gel electrolytes.
Figure 27 is linear polarisation curves when Zn electrode is contacted from different gel electrolytes.
Figure 28 is chronoamperometry (CA) measurement result when Zn electrode is contacted from different gel electrolytes.
Figure 29 is the figure indicated using chronoamperometry (CA) scanning electron microscope (SEM) image afterwards.
Figure 30 and Figure 31 is the figure of the circulation ability test result of battery in gel electrolyte.
Specific embodiment
The present invention provides a kind of battery, including anode, cathode and electrolyte, and the electrolyte includes electrolyte and can be molten
At least one of aqueous solution or the alcoholic solution for solving the electrolyte and making the electrolyte ionization；Wherein: the electrolyte
It further include polyethylene glycol.
The inventors discovered that polyethylene glycol dissolves in the electrolyte of battery, especially rechargeable water system hybrid battery
(ReHAB) electrolyte, and it is capable of providing the performance excellent to battery, this will be discussed later in more detail.In addition, in electrolyte
In include polyethylene glycol on the basis of further comprise fumed silica, with the gas phase titanium dioxide for individually making Electrolyte Gel
Silicon is compared, and gel time can be increased, and improves battery performance, this also will be discussed later in more detail.
In the present invention, the volume based on the electrolyte, the additive amount of the polyethylene glycol are 0.1~2 volume %,
Preferably 1~2 volume %, more preferably 1 volume %.If additive amount is lower than 0.1 volume % or is higher than 2 volume %,
The cycle performance of ReHAB significantly reduces.
In the present invention, polyethylene glycol is preferably selected from polyethylene glycol 200, Liquid Macrogol and polyethylene glycol 400 extremely
Few one kind.Polyethylene glycol can be commercially available, such as can be commercially available from Sigma Aldrich company.
It finds in the present invention, when the volume based on the electrolyte, the electrolyte includes: 1 volume % polyethylene glycol
200, when 2 volume % polyethylene glycol 200s, 1 volume % Liquid Macrogol or 1 volume % polyethylene glycol 400, electricity can be supplied to
The preferable performance in pond, this will be discussed in more detail below.
In the present invention, the electrolyte may further include fumed silica.Preferably, fumed silica by
Silicon tetrachloride is prepared by vapor phase method, can also be commercially available.
Vapor phase method is called pyrolysismethod, dry method or combustion method.Its raw material be silicon tetrachloride, oxygen and hydrogen, at high temperature instead
It should form.Reaction equation are as follows: SiCl4+2H2+O2→SiO2+4HCl.Air and hydrogen is overpressurized respectively, separated, cooled dehydrated,
Synthesis hydrolysis furnace is sent into after dry, dust removal and filtration.Silicon tetrachloride raw material is sent to rectifying column rectifying, heats and steams in evaporator
Hair, and using drying, filtered air as carrier, it send to synthesis and hydrolyzes furnace.It is and a certain amount of after silicon tetrachloride gasifies at high temperature
Hydrogen and oxygen carry out vapor phase hydrolysis at a high temperature of 1800 DEG C or so；The fumed silica generated at this time is amorphous
Ultra-fine grain, has a cyclic structure, and gel force is strong, high surface activity, can form the preferable silica gel of thixotropy.
In the present invention, the weight based on the electrolyte, the additive amount of the polyethylene glycol is 1~2 weight %, described
The additive amount of fumed silica is 3~4 weight %, preferably 3 weight %, 3.5 weight % or 4 weight %.If poly- second two
Not in the range, then the cycle performance of ReHAB significantly reduces the additive amount of pure and mild fumed silica.
In the present invention, it is preferred to the weight based on the electrolyte, the electrolyte includes: 1 weight % polyethylene glycol
200 and 4 weight % fumed silicas, 2 weight % polyethylene glycol 200s and 3 weight % fumed silicas, the 1 poly- second of weight %
The weight % of glycol 300 and 4 fumed silica, 2 weight % Liquid Macrogols and 3 weight % fumed silicas, 1 weight %
Polyethylene glycol 400 and 4 weight % fumed silicas or 2 weight % polyethylene glycol 400s and 3 weight % fumed silicas.
Using the combination of these polyethylene glycol and fumed silica, better battery performance can be obtained.This will be detailed below
Description.
The particle size range of the fumed silica is preferably 20nm hereinafter, preferably 3~20nm, more preferable 5~20nm,
Further preferred 5~15nm, still further preferred 5~10nm, still more preferably 7~10nm.If partial size is greater than 20nm,
The then gelatification that fumed silica generally can not bring into play, so that the excellent performance of battery generally can not be supplied to.
In addition, electrolyte of the invention can also include colloid stabilizer, to change the configuration of surface of micelle, prevention micelle
Aggregation and delay gelatinizing process, can effectively change the performance of colloid.
Colloid stabilizer can be selected from polyvinyl alcohol, dextrin, glycerol, polyacrylamide and fatty alcohol polyoxyethylene ether extremely
Few one kind.
Preferably, colloid stabilizer is polyacrylamide.The aquation point of gel electrolyte can be effectively relieved in polyacrylamide
Layer.In addition, polyacrylamide can also play the role of absorbing moisture, increase system viscosity, thus as a kind of viscosity modifier.
Anode includes plus plate current-collecting body and the positive active material for participating in electrochemical reaction, and positive active material can be reversible
Abjection-embedded ion；The material of plus plate current-collecting body is selected from one of carbon-based material, metal or alloy；Cathode includes at least negative
Pole collector；Electrolyte, which can ionize out at least one charge and discharge process, occurs reduction-deposition and oxidation-dissolution in cathode
Active ion.
The carrier that plus plate current-collecting body is only used as electronics to conduct and collect, is not involved in electrochemical reaction, i.e., works in battery electric
It presses in range, what plus plate current-collecting body can be stable is present in electrolyte without any side reaction generation, to guarantee battery
With stable cycle performance.
Positive active material participates in anode reaction in the present invention, and can it is reversible deviate from-embedded ion or functional group.
Preferably, positive active material can it is reversible deviate from-be embedded in lithium ion, sodium ion, zinc ion or magnesium ion.
Positive active material, which can be, meets general formula Li1+xMnyMzOkCan it is reversible deviate from-be embedded in the spinelle of lithium ion
The compound of structure, wherein -1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M be selected from Na, Li, Co, Mg,
At least one of Ti, Cr, V, Zn, Zr, Si, Al.Preferably, positive active material contains LiMn2O4.It is furthermore preferred that anode is living
Property substance contains the LiMn through overdoping or coating modification2O4。
Positive active material, which can be, meets general formula Li1+xMyM′zM″cO2+nCan it is reversible deviate from-be embedded in the layer of lithium ion
The compound of shape structure, wherein -1 < x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1, -0.2≤n≤0.2, M, M ', M "
It is respectively selected from least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al.Preferably, positive active material contains
LiCoO2。
Positive active material is also possible to meet general formula LixM1-yM′y(XO4)nCan it is reversible deviate from-be embedded in lithium ion
The compound of olivine structural, wherein 0 < x≤2,0≤y≤0.6,1≤n≤1.5, M are selected from Fe, Mn, V or Co, and M ' is selected from
At least one of Mg, Ti, Cr, V or Al, X are selected from least one of S, P or Si.Preferably, positive active material contains
LiFePO4。
In current Lithium Battery Industry, nearly all positive active material all can be through modifications such as overdoping, claddings.But
The means such as doping, coating modification cause the chemical general formula of material to express complicated, such as LiMn2O4It can not represent at present extensively
The general formula of " LiMn2O4 " that uses, and should be with general formula Li1+xMnyMzOkSubject to, it widely include by various modifications
LiMn2O4Positive active material.Likewise, LiFePO4And LiCoO2Also it should be construed broadly to include and be mixed by various
What miscellaneous, cladding etc. was modified, general formula corresponds with LixM1-yM′y(XO4)nAnd Li1+xMyM′zM″cO2+nPositive active material.
When positive active material of the invention is reversible abjection-insertion lithium ion compound, it can select such as LiMn2O4、
LiFePO4、LiCoO2、LiMxPO4、LiMxSiOyCompounds such as a kind of (wherein M are variable valency metal).In addition, can deviate from-be embedded in
The compound of sodium ion such as NaVPO4F can deviate from-be embedded in the compound such as γ-MnO of zinc ion2, can deviate from-it is embedded in magnesium ion
Compound such as MgMxOy(wherein M be a kind of metal, 0.5 < x <, 3,2 < y < 6) and have similar functions, can deviate from-it is embedding
The compound for entering ion or functional group all can serve as the positive active material of battery of the present invention.
It in a particular embodiment,, can also be as needed other than positive active material when preparing anode sizing agent
Add conductive agent and binder.
Conductive agent be selected from conducting polymer, active carbon, graphene, carbon black, carbon fiber, metallic fiber, metal powder and
One of sheet metal is a variety of.
Binder is selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, polyethers, fluorination
One of polymer, poly- divinyl polyethylene glycol, polyethyleneglycol diacrylate, glycol dimethacrylates, or
The mixture and derivative of above-mentioned polymer.In a specific embodiment, binder is selected from polytetrafluoroethylene (PTFE) (PTFE) or poly- inclined
Vinyl fluoride (PVDF).
Cathode includes at least negative current collector, and specific in embodiment, cathode can only include negative current collector, and
The carrier that negative current collector is only used as electronics to conduct and collect, is not involved in electrochemical reaction.The material of negative current collector is selected from gold
Belong at least one of Ni, Cu, Ag, Pb, Mn, Sn, Fe, Al, Zn or the above-mentioned metal Jing Guo Passivation Treatment or elemental silicon,
Or carbon-based material, wherein carbon-based material includes graphite material, such as the foil of commercialized graphite compacting, wherein shared by graphite
Weight ratio range be 90-100%.The material of negative current collector is also selected from the stainless of stainless steel or passivated processing
Steel.Stainless steel includes but are not limited to stainless (steel) wire and stainless steel foil, likewise, the model of stainless steel can be 300 series
Stainless steel, such as stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.
In addition, negative current collector is also selected from the plating/coating metal high containing hydrogen-evolution overpotential, to reduce cathode pair
The generation of reaction.Plating/coating is selected from least one in the simple substance containing C, Sn, In, Ag, Pb, Co, Zn, alloy or oxide
Kind.Plating/coating thickness range is 1-1000nm.Such as: the negative current collector surface of copper foil or graphite foil plate tin, lead or
Silver.
In addition, alcoholic solution includes but are not limited to ethyl alcohol or methanol.
Electrolyte, which can ionize out at least one charge and discharge process, occurs reduction-deposition and oxidation-dissolution in cathode
Active ion.
Active ion includes metal ion, and metal is selected from least one of Zn, Fe, Cr, Cu, Mn, Ni, Sn.
Metal ion is present in electrolyte in the form of chlorate, sulfate, nitrate, acetate, formates, phosphate etc.
In.Preferably, metal ion is to be present in electrolyte in the form of the mixture of sulfate, acetate or sulfate and acetate
In.
It preferably, further include a kind of electrolyte in electrolyte, electrolyte can ionize out at least one charge and discharge process
Anode can it is reversible deviate from-ion that is embedded in, to improve the ion-exchange speed in positive active material and electrolyte, from
And improve the high rate charge-discharge performance of the battery in the present invention.Specifically, positive active material be can it is reversible deviate from-be embedded in
The compound of lithium ion, electrolyte can also correspondingly ionize out lithium ion.The ion of reversible abjection-insertion include lithium ion or
Sodium ion or magnesium ion or zinc ion.
The charge-discharge principle of battery are as follows: deviate from the ion of reversible abjection-insertion when charging, in positive active material, simultaneously
It is oxidized with variable valency metal in positive active material, and ejected electron；Electronics reaches battery cathode, while electricity via external circuit
Active ion in solution liquid obtains electronics in negative current collector and is reduced, and is deposited on negative current collector.Discharge process is then
The inverse process of charging.
In the present invention, it in order to provide better security performance, is preferably gone back between positive electrode and negative electrode in the electrolytic solution
Equipped with diaphragm.Diaphragm can to avoid positive and negative anodes caused by other unexpected factors be connected and caused by short circuit.Diaphragm does not have special want
It asks, as long as permission electrolyte passes through and the diaphragm of electronic isolation.
Embodiment
Polyethylene glycol 200, Liquid Macrogol used in embodiment and polyethylene glycol 400 (be abbreviated as respectively " PEG200,
PEG300 and PEG400 ") it is commercially available from Sigma Aldrich.Fumed silica (partial size: 7nm) is from Sigma
Aldrich is commercially available.
[reference example 1]
[preparation of battery]
By LiMn2O4, conductive agent graphite (KS-6, AL-125, TIMCAL), binder Kynoar (PVDF, Kynar,
HSV900), mixed in water according to mass ratio 86:7:7, be mixed to form uniform anode sizing agent, anode sizing agent is coated in stone
Active material layer is formed on black foil, drying for 24 hours, is then carried out tabletting, anode is made at 60 DEG C.
Cathode is used as using the zinc foil (Rotometals, purity 99.6%) with a thickness of 0.2mm.Diaphragm is glass fibre
Diaphragm (AGM, Nippon Sheet Glass Co., Ltd., with a thickness of 1mm).Diaphragm and cathode size are suitable with anode.
Weigh the zinc sulfate (Alfa Aesar, >=98% purity) of certain mass, lithium sulfate (Sigma-Aldrich, >=
99% purity), it is added in deionized water and dissolves, be configured to the ginseng that sulfuric acid zinc concentration is 2mol/L, sulfuric acid lithium concentration is 1mol/L
Examine electrolyte 1.Adjusting and referring to the pH value of electrolyte 1 is about 4.
[embodiment 1]
Battery is prepared according to the step in [reference example 1], difference is: based on the body in [reference example 1] with reference to electrolyte 1
Product, adds 0.1 volume %PEG200 in reference electrolyte 1.
[embodiment 2]
Battery is prepared according to the step in [reference example 1], difference is: based on the body in [reference example 1] with reference to electrolyte 1
Product, adds 0.5 volume %PEG200 in reference electrolyte 1.
[embodiment 3]
Battery is prepared according to the step in [reference example 1], difference is: based on the body in [reference example 1] with reference to electrolyte 1
Product, adds 1 volume %PEG200 in reference electrolyte 1.
[embodiment 4]
Battery is prepared according to the step in [reference example 1], difference is: based on the body in [reference example 1] with reference to electrolyte 1
Product, adds 2 volume %PEG200 in reference electrolyte 1.
[embodiment 5]
Battery is prepared according to the step in [reference example 1], difference is: based on the body in [reference example 1] with reference to electrolyte 1
Product, adds 1 volume %PEG300 in reference electrolyte 1.
[embodiment 6]
Battery is prepared according to the step in [reference example 1], difference is: based on the body in [reference example 1] with reference to electrolyte 1
Product, adds 1 volume %PEG400 in reference electrolyte 1.
Test method:
1, chronoamperometry
Illustrate that Zn is deposited on anode when applying overvoltage using chronoamperometry.Test in three-electrode system into
Row, the three-electrode system is by about 2.5cm2The Zn working electrode (WE) of polishing, nickel foam are to electrode (CE) and SCE reference electrode
(RE) it forms.Zn electrode size is redefined after completing test, and is used for measurement current density (mAcm-2).It will be electric
Pole is connected on multichannel galvanostat (VMP3, Biologic).Then it keeps applying overvoltage 1 hour.Record the electric current generated
And as mAcm-2Drafting pattern.
2, scanning electron microscopy (SEM)
Using 5kV high voltage (EHT) by Field Emission Scanning Electron microscope (FE-SEM, Leo-1550,
Zeiss) working electrode (WE) after test is characterized.
3, corrosion research
By evaluating the Zn when contacting with different electrolytes using Tafel fitting algorithm to linear polarization (LP) data
Corrosive nature.These linear polarization (LP) data obtain as follows: usable floor area is about 5cm2Polishing Zn item as work electricity
Pole (WE), Pt are used as to electrode (CE) and SCE as reference electrode (RE).These three electrodes are put into 100mL three-neck flask, are filled out
Electrolyte is filled to preset graticule, so that Zn item submerges, the amount of electrolyte remains constant ensure that repeatable and comparable
Data.Electrode is connected on multichannel galvanostat (VMP3, Biologic).It is usual to apply EVT (voltage vs. time) step
24 hours, until the potential difference between working electrode (WE) and reference electrode (RE) is stablized.Apply between -0.02 to+0.02V
Linear polarization (LP) scanning, and be compared with the EVT voltage obtained from previous step, sweep speed 0.1mVs-1.It should
Linear polarization (LP) is tested in triplicate.It will intend for the second time with the data of third time linear polarization (LP) scanning for Tafel
It closes.By the way that corrosion current is calculated corrosion-current density (mAcm divided by working electrode (WE) area-2)。
4, battery performance is studied
Electrochemical test is carried out by Swagelok battery and button cell.Each battery is separated by AGM diaphragm
LiMn2O4/ KS-6/PVdF composite cathode and the zinc metal anode of polishing composition.Gel electrolyte (about 0.4g) is put into diaphragm.
Test is various in multichannel cell tester (BTS-5V5mA and BTS-5V10mA, Neware) between 1.4V and 2.1V voltage
(1C is defined as 115mAhg to charge-discharge performance-1).By multichannel galvanostat (VMP3, Biologic) in 1.4~2.1V
vs.Zn2+/Zn°, in 0.1mVs-1Sweep speed under carry out cyclic voltammetry (CV) test.All electrochemical datas are 20
DEG C obtain.
Test includes the circulation ability under C- rate capability, floating current density, open-circuit voltage and 1C or 4C.
Test result is as follows.
Erosion analysis result when Fig. 1 shows when Zn anode with the electrolyte including PEG and contacts with reference to electrolyte 1
(Tafel curve).
From the results, it was seen that control sample is the curve of the leftmost side, there is most deep current potential.When containing in electrolyte
When PEG, equilibrium potential rises under all scenario.In electrolyte comprising 1 volume %PEG200 show it is best as a result, electrolyte
In also show preferable result comprising 2 volume %PEG200,1 volume %PEG300 or 1 volume %PEG400.Similarly, right
The corrosion electric current density of product is also highest in the same old way.PEG, which is added in electrolyte, reduces corrosion current, this is beneficial for battery
's.Show best comprising 1 volume %PEG200 in electrolyte as a result, including 2 volume %PEG200,1 body in electrolyte
Product %PEG300 or 1 volume %PEG400 also shows preferable result.
Chronoamperometry result: in the series, overpotential is arranged in -135mV.Fig. 2 and Fig. 3 shows measurement knot
Fruit.From which it can be seen that with it is all comprising the electrolyte of PEG compared with, it is exhausted to give higher current density with reference to electrolyte 1
To value.Thus may determine that a possibility that PEG by inhibiting the tree-shaped crystallization on Zn to be formed to some extent.As can be seen that increasing
The concentration of PEG200 will reduce the absolute value of depositing current density.In addition, the molecular weight of PEG from 200 increase to 400 will also decrease it is heavy
The absolute value of product current density.
Fig. 4 shows very important result, shows not interfere Zn removing/deposition dynamics, but more preferable.This
Outside, current potential is moved upwards up to almost 110mV.This facilitates battery and releases further away from hydrogen.It can be expected that hydrogen from battery
In releasing reduce very significantly.The result is consistent with corrosivity result (balance corrosion potential moves up).
The presence that Fig. 5 can be seen that 1 volume %PEG200 compared with Fig. 6 increases the polarization in battery slightly, this
Also Li is affected+Dynamics of the insertion/extraction in battery inside/outside.In order to further evaluate, battery data will be shown below.
Rate capability result: so that battery is carried out 5 circulations at 0.2C, 0.5C, 1C, 2C and 4C respectively, then return
5 circulations are carried out under 0.2C.Fig. 7 shows the ReHAB battery in the case where reference electrolyte 1 includes various concentration PEG200
Discharge capacity result.Fig. 8 is shown in the reference electrolyte 1 of the PEG200 in reference electrolyte 1 and comprising different molecular weight,
The discharge capacity result of ReHAB battery.
As can be seen that the discharge capacity of battery can be improved in 1 volume %PEG200 compared with reference electrolyte 1.
Floating charge characterization result: it charges 72 hours at 2.1V to button cell under constant-voltage mode.In Fig. 9 and Figure 10
In have recorded packet the battery with or without PEG charging capacity.As can be seen that all electrolyte comprising PEG all make floating charge
Capacity increases.1 volume %PEG200 has floating charge capacity very similar compared with control sample.It shows best knot
Fruit, because not will lead to any reduction of floating charge performance.
Open-circuit voltage monitored results: keeping button cell fully charged, so that it is dallied 72 hours, continuously records their open circuit
As a result voltage is plotted in Figure 11.
Circulation ability test result: in 1C, 300 circulations, CC-CV, 10% current interruptions, 1.4-2.1 V vs.Zn2+/
The test is carried out by button cell and big battery under Zn.Figure 12 and Figure 13 show button cell as a result, Figure 14 is shown
The result of big battery.
As can be seen that the use of PEG, the use of especially 1 volume %PEG200 increase the discharge capacity of button cell.
Especially as shown in Figure 14, the use of 1 volume %PEG200 obtains significant result in big battery.It is recycled at 300
Afterwards, big battery is shown more than 122mAh/g.
Figure 15 show at -135mV using chronoamperometry (CA) after 3 hours button cell circulation ability.
Inventors noted that using the sample after chronoamperometry have than they using the correspondence before chronoamperometry
The higher initial discharge capacity of object.This is attributed to the tree generation grown in advance on the surface by chronoamperometry step
Additional surface area.It, should compared with using the sample before chronoamperometry due to the unstability that surface tree generates
Capacity more quickly reduces.
For the sample comprising 1 volume %PEG200, although with the sample after chronoamperometry capacity with compared with
It reduces at high speed, but they still are able to complete entire recycle scheme 1000 times circulations at 4C.However, observation control
The sample of electrolyte assembling, inventor notice that capacity has greatly in about 190 circulations using the sample after chronoamperometry
Decline, and all fail in about 450 circulations.
Generally speaking, the use of PEG increases the corrosion resistance of electrode in electrolyte, improves the performance of battery, especially
It is battery capacity and long-time cyclical stability.
[comparative example 1]
Battery is prepared according to the step in [reference example 1], difference is: based on the weight in [reference example 1] with reference to electrolyte 1
Amount, adds 5 weight % fumed silicas (FS) in reference electrolyte 1.
[embodiment 7]
Battery is prepared according to the step in [reference example 1], difference is: based on the weight in [reference example 1] with reference to electrolyte 1
Amount, adds 1 weight %PEG200 and 4 weight % fumed silicas (FS) in reference electrolyte 1.
[embodiment 8]
Battery is prepared according to the step in [reference example 1], difference is: based on the weight in [reference example 1] with reference to electrolyte 1
Amount, adds 2 weight %PEG200 and 3 weight % fumed silicas (FS) in reference electrolyte 1.
[embodiment 9]
Battery is prepared according to the step in [reference example 1], difference is: based on the weight in [reference example 1] with reference to electrolyte 1
Amount, adds 1 weight %PEG300 and 4 weight % fumed silicas (FS) in reference electrolyte 1.
[embodiment 10]
Battery is prepared according to the step in [reference example 1], difference is: based on the weight in [reference example 1] with reference to electrolyte 1
Amount, adds 2 weight %PEG300 and 3 weight % fumed silicas (FS) in reference electrolyte 1.
[embodiment 11]
Battery is prepared according to the step in [reference example 1], difference is: based on the weight in [reference example 1] with reference to electrolyte 1
Amount, adds 1 weight %PEG400 and 4 weight % fumed silicas (FS) in reference electrolyte 1.
[embodiment 12]
Battery is prepared according to the step in [reference example 1], difference is: based on the weight in [reference example 1] with reference to electrolyte 1
Amount, adds 2 weight %PEG400 and 3 weight % fumed silicas (FS) in reference electrolyte 1.
Figure 16 shows linear polarisation curves when Zn electrode is contacted with different electrolytes.
Table 1 shows the corrosion electric current density and equilibrium potential of the reference example 1 of measurement, comparative example 1 and embodiment 7 to 12
(vs.SCE)
Table 1
It can be seen that the increase with PEG molecular weight from Figure 16 and table 1, will have better corrosion protection.It is higher
PEG wt% will also have better corrosion protection.
The electric current obtained when contacting Figure 17 shows Zn electrode with above-mentioned different electrolytes using chronoamperometry (CA) is close
Degree.
Figure 18 to Figure 25 respectively illustrates the battery of reference example 1, comparative example 1 and embodiment 7 to embodiment 12 using meter
When current method (CA) afterwards electrode SEM figure.
Schemed from these SEM as can be seen that the deposition of Zn is much flat when using FS-PEG gel electrolyte.This also leads to
The low absolute value for crossing CA current density is confirmed.
Circulation ability test result: in 1C, CC-CV, 10% current interruptions, 1.4-2.1V vs.Zn2+It is somebody's turn to do under/Zn
Test.Figure 26 shows test result.
As can be seen that significantly increasing circulation ability using FS-PEG gel, increase by 15% after 300 circulations.4 weights
Amount %FS+1 weight %PEG300 obtains best circulation ability.
Generally speaking, FS-PEG gel significantly improves the circulation ability of battery.Also, FS-PEG gel significantly reduces
Tree-shaped crystallization on Zn is formed.
[reference example 2]
[preparation of battery]
Using raw material identical with reference example 1 and step preparation anode and cathode, and using identical with reference example 1
Diaphragm.
Weigh the zinc sulfate (Alfa Aesar, >=98% purity) of certain mass, lithium sulfate (Sigma-Aldrich, >=
99% purity), it is added in deionized water and dissolves, be configured to the ginseng that sulfuric acid zinc concentration is 1mol/L, sulfuric acid lithium concentration is 2mol/L
Examine electrolyte 2.Adjusting and referring to the pH value of electrolyte 2 is about 4.
[comparative example 2]
Battery is prepared according to the step in [reference example 2], difference is: based on the weight in [reference example 2] with reference to electrolyte 2
Amount, adds 5 weight % fumed silicas (FS) in reference electrolyte 2.
[embodiment 13]
Battery is prepared according to the step in [reference example 2], difference is: based on the weight in [reference example 2] with reference to electrolyte 2
Amount, adds 1 weight %PEG200 and 4 weight % fumed silicas (FS) in reference electrolyte 2.
[embodiment 14]
Battery is prepared according to the step in [reference example 2], difference is: based on the weight in [reference example 2] with reference to electrolyte 2
Amount, adds 2 weight %PEG200 and 3 weight % fumed silicas (FS) in reference electrolyte 2.
[embodiment 15]
Battery is prepared according to the step in [reference example 2], difference is: based on the weight in [reference example 2] with reference to electrolyte 2
Amount, adds 1 weight %PEG300 and 4 weight % fumed silicas (FS) in reference electrolyte 2.
[embodiment 16]
Battery is prepared according to the step in [reference example 2], difference is: based on the weight in [reference example 2] with reference to electrolyte 2
Amount, adds 2 weight %PEG300 and 3 weight % fumed silicas (FS) in reference electrolyte 2.
[embodiment 17]
Battery is prepared according to the step in [reference example 2], difference is: based on the weight in [reference example 2] with reference to electrolyte 2
Amount, adds 1 weight %PEG400 and 4 weight % fumed silicas (FS) in reference electrolyte 2.
[embodiment 18]
Battery is prepared according to the step in [reference example 2], difference is: based on the weight in [reference example 2] with reference to electrolyte 2
Amount, adds 2 weight %PEG400 and 3 weight % fumed silicas (FS) in reference electrolyte 2.
Figure 27 shows linear polarisation curves when Zn electrode is contacted with different electrolytes.
Table 2 shows the corrosivity data of the battery using above-mentioned electrolyte.
Table 2
As can be seen that with reference to 5 weight %FS (comparative example 2) corrosion rates with higher are added in electrolyte 2, it is lower
Equilibrium potential, it means that than being more corrosive with reference to electrolyte 2 (reference example 2).When PEG is added, corrosion is reduced, with
The increase of PEG molecular weight will have better corrosion protection.Higher PEG wt% will also have better corrosion protection.
Figure 28 shows chronoamperometry (CA) measurement result of Zn electrode when contacting with above-mentioned different electrolytes.
Figure 29 show using chronoamperometry (CA) afterwards electrode SEM figure.
Generally speaking, the presence of PEG makes the absolute value of CA electric current become smaller.Can determine form tree-shaped crystallization on Zn can
Energy property becomes smaller.The SEM of commercially available Zn shows that the material has a some holes, this is probably derived from foundry engieering.When using with reference to electrolysis
When liquid 2, deposit looks like chunk, and diameter is about 20 μm.If continuing to deposit, those chunks will become tree-shaped crystallization
Zn.The deposition of Zn from 5 weight %FS (comparative example 2) shows layer structure, it means that lesser tree-shaped crystalline growth
A possibility that.Deposit on electrode containing PEG be it is laminar, this is best result.
Circulation ability test result: in 4C, CC-CV, 1000 circulations, 10% current interruptions, 1.4-2.1 V vs.Zn2+/
The test is carried out by button cell under Zn.Figure 30 and Figure 31 show test result.
Generally speaking, when in electrolyte including PEG, when especially including PEG and fumed silica, electrode is increased
Corrosion resistance, improve the performance of battery, especially battery capacity and circulation ability.
Claims (13)
1. a kind of battery, including anode, cathode and electrolyte, the electrolyte include electrolyte and can dissolve the electrolyte
And at least one of aqueous solution or the alcoholic solution for making the electrolyte ionization；It is characterized by: the electrolyte further includes
Polyethylene glycol.
2. battery according to claim 1, it is characterised in that: the volume based on the electrolyte, the polyethylene glycol
Additive amount is 0.1~2 volume %.
3. battery according to claim 2, it is characterised in that: the volume based on the electrolyte, the polyethylene glycol
Additive amount is 1~2 volume %.
4. battery according to any one of claim 1-3, it is characterised in that: the volume based on the electrolyte, it is described
The additive amount of polyethylene glycol is 1 volume %.
5. battery according to any one of claim 1-3, it is characterised in that: the polyethylene glycol is selected from polyethylene glycol
200, at least one of Liquid Macrogol and polyethylene glycol 400.
6. battery according to claim 5, it is characterised in that: the volume based on the electrolyte, the electrolyte include:
1 volume % polyethylene glycol 200,2 volume % polyethylene glycol 200s, 1 volume % Liquid Macrogol or 1 volume % polyethylene glycol 400.
7. battery according to claim 1, it is characterised in that: the electrolyte further comprises fumed silica.
8. battery according to claim 7, it is characterised in that: the weight based on the electrolyte, the polyethylene glycol
Additive amount is 1~2 weight %, and the additive amount of the fumed silica is 3~4 weight %.
9. battery according to claim 8, it is characterised in that: the weight based on the electrolyte, the electrolyte include:
1 weight % polyethylene glycol 200 and 4 weight % fumed silicas, 2 weight % polyethylene glycol 200s and 3 weight % gas phase titanium dioxides
Silicon, 1 weight % Liquid Macrogol and 4 weight % fumed silicas, 2 weight % Liquid Macrogols and 3 weight % gas phases two
Silica, 1 weight % polyethylene glycol 400 and 4 weight % fumed silicas or 2 weight % polyethylene glycol 400s and 3 weights
Measure % fumed silica.
10. battery according to claim 7, it is characterised in that: the partial size of the fumed silica is 20nm or less.
11. battery according to claim 1, the anode includes that plus plate current-collecting body and the anode of participation electrochemical reaction are living
Property substance, the positive active material can it is reversible deviate from-embedded ion；The cathode includes at least negative current collector；It is described
Electrolyte, which can ionize out at least one charge and discharge process, occurs reduction-deposition and oxidation-dissolution activity in the cathode
Ion, the active ion include metal ion, and the metal is selected from least one of Zn, Fe, Cr, Cu, Mn, Ni, Sn.
12. battery according to claim 11, it is characterised in that: the metal ion is with sulfate, acetate or sulfuric acid
The form of the mixture of salt and acetate is present in the electrolyte.
13. battery according to claim 11, it is characterised in that: the positive active material can it is reversible deviate from-be embedded in
Lithium ion, sodium ion, zinc ion or magnesium ion.
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| CN113285126A (en) * | 2021-04-13 | 2021-08-20 | 中国电力科学研究院有限公司 | Colloidal electrolyte and preparation method thereof |
| CN111403829B (en) * | 2020-04-24 | 2021-10-01 | 中国科学院上海硅酸盐研究所 | Water system gel state electrolyte with low-temperature working characteristic, pole piece additive and solid sodium ion battery |
| CN113725500A (en) * | 2021-09-03 | 2021-11-30 | 中南大学 | Mixed electrolyte of water-based zinc ion battery |
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