CN106549189A - Battery, set of cells and uninterrupted power source - Google Patents
Battery, set of cells and uninterrupted power source Download PDFInfo
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- CN106549189A CN106549189A CN201610638189.6A CN201610638189A CN106549189A CN 106549189 A CN106549189 A CN 106549189A CN 201610638189 A CN201610638189 A CN 201610638189A CN 106549189 A CN106549189 A CN 106549189A
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a kind of battery, including positive pole, negative pole and aqueous electrolyte, the positive pole includes positive active material and plus plate current-collecting body；The aqueous electrolyte includes the first metal ion and/or the second metal ion, first metal ion reversible can be deviate to be embedded in the positive pole in charge and discharge process, second metal ion is deposited as the second metal in the cathodic reduction in charging process, and second metal oxidation dissolution in discharge process is the second metal ion；The negative pole includes the negative material with loose structure, and the negative material includes zinc active material and negative electrode binder.The present invention can be effectively improved the dendrite problems of battery cathode, increase the cycle life of battery, improve the chemical property and security performance of battery.
Description
Technical field
The invention belongs to electrochemical energy storage field, and in particular to a kind of battery.
The invention further relates to a kind of set of cells, set of cells includes several batteries.
The invention further relates to a kind of uninterrupted power source.
Background technology
Lead-acid battery, which goes out to have surpassed a century, possesses the battery technology of maturation, in occupation of automobile starting storage battery, electronic
The absolute market share in the energy storage such as bicycle, UPS field.Although lead-acid battery service life cycle is relatively low, energy density also phase
To relatively low, but possess that price is very cheap, the very high advantage of cost performance.Therefore, in the last few years, Ni-MH battery, lithium ion
Battery, sodium-sulphur battery, flow battery etc., cannot replace lead-acid battery in energy storage field.
Occurred a kind of new aqoue seconary battery in recent years.The positive pole of the secondary cell can be based on the first metal ion
Reversible abjection-insertion reaction is carried out, it is anti-that negative pole can carry out reversible reduction deposition-oxidation dissolving based on the second metal ion
Should, electrolyte contains the second of the first metal ion and participation cathode deposition-dissolving reaction for participating in positive pole abjection-insertion reaction
Metal ion.The electrolyte of the type battery is aqueous solution, and the safety that there is no organic electrolyte in similar lithium ion battery is hidden
Suffer from, and it is environmentally friendly, cost is relatively low, and energy density is high.Therefore, the type battery promises to be replacement lead-acid battery very much
Energy-storage battery of future generation, with great using value.
Second metal ion of the type battery can be zinc ion, and now negative electrode active material is metallic zinc, but this
Class negative electrode active material in aqueous discharge and recharge when there are problems that so that the cycle performance of battery, charge and discharge electric capacity
Amount is affected.Therefore, prior art needs further to improve.
The content of the invention
The technical problem to be solved is to provide a kind of battery, battery cathode dendrite problems be improved significantly,
So as to improve the cycle life of battery, battery performance is improved.
For achieving the above object, the technical solution adopted in the present invention is as follows：A kind of battery, including positive pole, negative pole and water
It is electrolyte, the positive pole includes positive active material and plus plate current-collecting body；The aqueous electrolyte includes the first metal ion
And/or second metal ion, first metal ion in charge and discharge process the positive pole can it is reversible deviate from-be embedded in,
Second metal ion is deposited as the second metal in the cathodic reduction in charging process, and second metal was discharging
In journey, oxidation dissolution is the second metal ion；The negative pole includes the negative material with loose structure, the negative material bag
Include zinc active material and negative electrode binder.
Preferably, the negative pole also includes that with mesh-structured negative current collector the negative material is carried on described
On negative current collector.
Preferably, the range of aperture size of the mesh of the negative current collector is 0.3 millimeter -1.5 millimeters, the negative pole collection
The thickness range of fluid is 0.01 millimeter -0.5 millimeter.
Preferably, the zinc active material includes zinc and zinc compound, and the zinc compound includes Zinc Oxide, hydrogen-oxygen
Change zinc and at least one in zinc salt, wherein it is 0- that the zinc compound accounts for the weight/mass percentage composition of the negative material
50%.
Preferably, the preparation method of the negative pole is comprised the following steps：By zinc and/or zinc compound and negative electrode binder
It is dispersed in water, is uniformly mixing to obtain cathode size；The cathode size is coated on the negative current collector, is dried, is rolled
Pressure, shearing；The zinc load for obtaining and nickel positive pole are placed in the potassium hydroxide solution of 2-7mol/L, it is permanent with 2.1V constant pressures, 0.2C
Current charge, charges to the 100%-150% that charging capacity reaches the Zinc Oxide theoretical capacity, and the washing zinc load is into
Property.
Preferably, the negative electrode binder accounts for the weight/mass percentage composition of the negative material less than 7%.
Preferably, the negative electrode binder includes polyvinyl alcohol (PVA), hydroxypropyl methyl cellulose (HPMC), polypropylene
One or more in amide (PAM), politef (PTFE), Kynoar (PVDF).
Preferably, the negative material also includes additive, and the additive accounts for the quality percentage of the negative material and contains
Amount is less than 5%.
Preferably, the additive is selected from lead, indium, bismuth, the oxide of calcium or hydroxide or salt.
Preferably, the negative material also includes conductive agent, and the conductive agent accounts for the quality percentage of the negative material and contains
Amount is less than 5%.
Preferably, the conductive agent is selected from one or more in metallic nickel, metallic copper, conductivity ceramics.
Preferably, the conductive agent in activated carbon, graphite, carbon black, CNT, Graphene and its oxide one
Plant or several.
Preferably, the conductive agent is selected from the mixture or activated carbon and the mixture of CNT of activated carbon and graphite.
Preferably, the selection of the negative current collector includes copper, lead, the copper for being coated with lead, indium, bismuth or stannum, ferrum or rustless steel.
Preferably, first metal ion includes lithium ion, sodium ion or magnesium ion.
Preferably, second metal ion includes zinc ion.
Preferably, the pH value of the aqueous electrolyte is 3-7.
Present invention also offers a kind of set of cells, including several batteries as above.
Present invention also offers a kind of uninterrupted power source, including battery as above.
Compared with prior art, the invention has the beneficial effects as follows：The battery that the present invention is provided has porous negative pole, and porous is born
Has larger surface area, negative pole polarization, reduces the formation of dendrite during so as to reducing charging.Meanwhile, porous negative pole is tied at which
A large amount of electrolyte can be stored inside structure, internal liquid-solid interface area is much larger than the area on surface, so as to going back for zinc ion
Original is more carried out inside porous negative pole, so as to further reduce the formation of dendrite, so as to increase the cycle life of battery, from
And improve the chemical property and security performance of battery.
Specific embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention, is not intended to limit the present invention.
A kind of battery, including positive pole, negative pole and aqueous electrolyte, positive pole include positive active material and plus plate current-collecting body；
Aqueous electrolyte includes the first metal ion and/or the second metal ion, and the first metal ion is in charge and discharge process in positive pole
Can it is reversible deviate from-be embedded in, the second metal ion is deposited as the second metal in cathodic reduction in charging process, and the second metal exists
In discharge process, oxidation dissolution is the second metal ion；Negative pole includes the negative material with loose structure, and negative material includes
Zinc active material and negative electrode binder.
Positive active material participate in positive pole reaction, and can it is reversible deviate from-be embedded in the first metal ion.
Positive active material can meet 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 selected from Na, Li, Co, Mg, Ti,
At least one in Cr, V, Zn, Zr, Si, Al.Preferably, positive active material contains LiMn2O4。
Positive active material can meet 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 " point
Not Xuan Zi Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al at least one of.Preferably, positive active material contains
LiCoO2。
Positive active material can also be and meet 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 be selected from Fe, Mn, V or Co, M ' selected from Mg,
At least one of Ti, Cr, V or Al, at least one of the X in S, P or Si.Preferably, positive active material contains
LiFePO4。
In current battery industry, nearly all positive active material all can be through modifications such as doping, claddings.But mix
Miscellaneous, the means such as coating modification cause the chemical general formula of material to express complicated, such as LiMn2O4Can not represent extensively makes at present
The formula of " LiMn2O4 ", and should be with formula Li1+xMnyMzOkIt is defined, widely includes through various modified LiMn2O4
Positive active material.Likewise, LiFePO4And LiCoO2Should also be construed broadly to include through various doping, cladding etc.
Modified, formula corresponds with LixM1-yM′y(XO4)nAnd Li1+xMyM′zM″cO2+nPositive active material.
When positive active material is the material of the reversible abjection of energy-embedded lithium ion, preferably can be from such as LiMn2O4、
LiFePO4、LiCoO2、LiMxPO4、LiMxSiOyCompounds such as a kind of (wherein M are variable valency metal).
It is furthermore preferred that positive active material is LiMn2O4.In numerous positive electrodes, LiMn2O4It is considered as most
One of positive electrode of prospect, because it has the advantages that low cost, raw material abundance, environmental friendliness, safety are good.
Additionally, the compound of sodium ion can be deviate from-is embedded in (such as NaVPO4F), can deviate from-be embedded in the compound of magnesium ion
(such as MgMxOy(wherein M be a kind of metal, 0.5<x<3,2<y<6)) and have similar functions, can deviate from-embedded ion or
The compound of functional group can serve as the positive active material of battery of the present invention.
In a particular embodiment, when preparing positive electrode, in addition to positive active material, just generally can also add
Pole conductive agent and positive electrode binder are lifting the performance of positive pole.
Positive conductive agent can reduce the resistance of overall positive pole, while strengthening the conductive path between positive electrode granule.Just
Pole conductive agent is selected from conducting polymer, conductive oxide, conductivity ceramics, activated carbon, Graphene, carbon black, graphite, carbon fiber, gold
One or more in category fiber, metal dust and foil.Preferably, positive conductive agent accounts for the quality of positive electrode
Percentage ratio is 1%-15%.Further, positive conductive agent is graphite, and positive conductive agent accounts for the mass percent of positive electrode
For 10%-14%.
Positive electrode binder is conducive to making positive active material and conductive agent uniformly be bonded together, and just to be formed so as to process
Pole.Positive electrode binder can be selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, polyethers, fluorine
One kind in fluidized polymer, poly- divinyl Polyethylene Glycol, polyethyleneglycol diacrylate, glycol dimethacrylates,
Or the mixture and derivant of above-mentioned polymer.It is furthermore preferred that positive electrode binder is selected from politef (PTFE), polyvinylidene fluoride
Alkene (PVDF) or butadiene-styrene rubber (SBR).
Specifically, positive pole also includes the plus plate current-collecting body of load positive active material, and plus plate current-collecting body is only passed as electronics
The carrier led and collect, is not involved in electrochemical reaction, i.e., in the range of battery operating voltage, what plus plate current-collecting body can be stable deposits
Substantially there is no side reaction in being electrolyte, so as to ensure that battery has stable cycle performance.
The one kind of the material of plus plate current-collecting body in carbon-based material, metal or alloy.
The one kind of carbon-based material in vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.
Preferably, plus plate current-collecting body includes carrier and the graphite foil being coated on carrier.
In the present invention, use graphite foil as plus plate current-collecting body, not only alleviate the weight of positive pole, and in water system electricity
Graphite foil good stability in solution liquid, makes battery have higher float life, while reducing battery cost, possesses battery
The prospect of commercial applications.
Carrier electrochemicaUy inert itself, primarily serves the effect for carrying graphite foil, so as to improve the mechanical performance of graphite foil.
The material of carrier is selected from polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polyamide, poly- ammonia
One kind in carbamate, polyacrylonitrile.These polymeric materials can be stable be present in plus plate current-collecting body in and be not involved in
Electrochemical reaction, is that weight is saved in the higher energy density output of battery.Preferably, carrier is nylon wire, i.e. polyamide.
Metal includes Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or in the above-mentioned metal of Passivation Treatment one
Kind.
Alloy includes rustless steel, carbon steel, Al alloys, Ni alloys, Ti alloys, Cu alloys, Co alloys, Ti-Pt alloys, Pt-
Rh alloys or the one kind in the above-mentioned metal of Passivation Treatment.
Rustless steel includes stainless (steel) wire, stainless steel foil, and stainless model includes but are not limited to stainless steel 304 or not
One kind in rust steel 316 or Stainless steel 316 L.
Preferably, process is passivated to plus plate current-collecting body, its main purpose is that the surface for making plus plate current-collecting body forms one
The oxide-film of layer passivation, so as to stable collection and conduction electronics in battery charge and discharge process, can be played a part of, without
Participate in cell reaction, it is ensured that battery performance is stable.Plus plate current-collecting body deactivating process for the treatment of includes chemical passivation process or electrochemistry
Passivation Treatment.
Negative pole includes the negative material with loose structure, and negative material includes zinc active material and negative electrode binder.
In one embodiment, zinc active material is zinc.
In another embodiment, zinc active material includes zinc and zinc compound, and wherein zinc compound accounts for negative pole thing
The weight/mass percentage composition of matter is 0-50%.Zinc compound includes at least one in Zinc Oxide, zinc hydroxide and zinc salt.Zinc salt
Include but are not limited to zinc sulfate, zinc chloride, zinc acetate and zinc oxalate.Specifically, the preparation method of negative pole is comprised the following steps：
Zinc and/or zinc compound, binding agent are dispersed in water, cathode size is uniformly mixing to obtain；By cathode size
It is coated on negative current collector, is dried, rolls, shears.
The negative pole that shearing is obtained is carried out into tank formation, specifically, negative pole and nickel positive pole the hydroxide of 2-7mol/L is placed in into
In potassium solution, with 2.1V constant pressures, 0.2C constant-current charges, charge to charging capacity and reach Zinc Oxide theoretical capacity in negative pole
100%-150%, washing negative pole are given over to standby to neutrality.
The negative pole that shearing is obtained is carried out into tank formation, it is therefore an objective to which zinc compound is reduced into into zinc, while in the mistake of reduction
The negative material being carried on negative current collector is caused to become porous in journey, with big specific surface area.Ideally alienation
If completed into 100%, then the zinc compound in negative material is that Restore All contains into the quality of zinc, i.e. zinc compound
Measure as 0；But preferable 100% chemical conversion state is extremely difficult under normal circumstances, it is that monitoring is filled in chemical conversion in the present invention
Come the degree that judges to be melted into, in this case, zinc compound might have certain residual to the value of capacitance, i.e., final chemical conversion knot
In the negative material of the negative pole after beam, the weight/mass percentage composition of zinc compound is 0-50%.Certainly, those skilled in the art are public
Know, the scope that the weight/mass percentage composition of zinc compound in negative material can be made by controlling the chemical conversion time to exceed 50%,
But if avoid the scope, still fall within the present invention concept in.
The density of the density ratio zinc of Zinc Oxide is little by nearly 30%, and the volume of the Zinc Oxide of phase homogenous quantities is much larger than the body of zinc
Product, when zinc load is prepared, zinc source adopts zinc and/or zinc compound, then obtained porous negative pole is melted into, will be contained
Zinc compound is reduced into zinc, and the surface area of the porous zinc load for obtaining significantly greater than did not entered the zinc load of chemical conversion, therefore, can
During further reducing charging, negative pole polarization, reduces the formation of dendrite.
Preferably, negative material also includes additive, and additive can improve the corrosion of zinc load, so as to improve zinc load
Chemical property.
Specifically, additive accounts for the weight/mass percentage composition of negative material less than 5%.Additive is selected from lead, indium, bismuth, calcium
Oxide or hydroxide or salt in one or more.In a preferred embodiment, additive is simultaneously using oxidation
Lead, Indium sesquioxide. and calcium hydroxide.
Preferably, negative material also includes conductive agent, and what conductive agent can increase negative material leads electronic capability, so as to drop
The internal resistance of low zinc load.
Specifically, conductive agent accounts for the weight/mass percentage composition of negative material less than 5%.Conductive agent is selected from metallic nickel, metal
One or more in copper, conductivity ceramics.Preferably, conductive agent is so arranged using the carbon-based material with high-specific surface area,
That not only can improve negative material leads electronic capability, can also further make negative material more porous.Carbon-based material includes
One or more in activated carbon, graphite, carbon black, CNT, Graphene and its oxide.Example, carbon black includes acetylene
Black and Super P.
Specifically, negative electrode binder is selected from politef (PTFE), Kynoar (PVDF), hydroxypropyl methyl fiber
One or more in plain (HPMC), polyvinyl alcohol (PVA), polyacrylamide (PAM), or carboxymethyl cellulose (CMC) and fourth
Benzene rubber (SBR).Negative electrode binder accounts for the weight/mass percentage composition of negative material and is less than 7%.
Preferably, negative pole also includes that with mesh-structured negative current collector negative material is carried on negative current collector.
In negative electrodes are prepared, the mode that cathode size is coated on negative current collector is not particularly limited, at one
In specific embodiment, by slurry, cathode size is coated on negative current collector.
The range of aperture size of the mesh of negative current collector is 0.3-1.5 millimeters, preferably 0.8-1 millimeters.Negative pole currect collecting
The thickness range of body is 0.01-0.5 millimeters, and in the case where disclosure satisfy that the precursor to form hanging, negative current collector gets over Bao Yuehao.Negative pole
The selection of collector includes copper, lead, the copper for being coated with lead, indium, bismuth or stannum, ferrum or rustless steel.Preferably, negative current collector is selected from punching
Hole Copper Foil or oblique pull copper mesh.
Aqueous electrolyte includes electrolytic salt and aqueous solvent.Wherein, in electrolyte, the purpose of aqueous solvent is dissolving electrolysis
Matter salt, and electrolytic salt is ionized in a solvent, cation and the anion that can move freely finally is generated in the electrolytic solution.
Aqueous electrolyte includes the first metal ion or the second metal ion, or the first metal ion and the second metal from
Son.
In aqueous electrolyte the first included metal ion in charge and discharge process positive pole can it is reversible deviate from-it is embedding
Enter.I.e. when battery charges, the first metal ion is deviate from from positive active material, into electrolyte；In battery discharge, electricity
In the embedded positive active material of the first metal ion in solution liquid.In embodiment of the aqueous electrolyte only including the first metal ion
In, battery is worked first as electric discharge.
Preferably, the first metal ion is selected from lithium ion, sodium ion or magnesium ion.It is furthermore preferred that the first metal ion is
Lithium ion.
Also include the second metal ion in aqueous electrolyte, the second metal ion is deposited in cathodic reduction in charging process
For the second metal, in discharge process, the second metal is aoxidized and is dissolved as the second metal ion.Specifically, the second metal ion is zinc
Ion.In embodiment of the aqueous electrolyte only including the second metal ion, battery is worked first to charge.
In the embodiment that aqueous electrolyte includes the first metal ion and the second metal ion simultaneously, battery is worked first
Both can be charge can also be electric discharge.Preferably, the first metal ion is different from the second metal ion.In the side of being preferable to carry out
Under formula, in aqueous electrolyte, include lithium ion and zinc ion simultaneously.In charge and discharge process, lithium ion positive pole occur it is embedded-
There is deposition-dissolving in negative pole in abjection, zinc ion.
Anion in aqueous electrolyte, can be it is any have substantially no effect on both positive and negative polarity reaction, and electrolytic salt molten
The anion dissolved in agent.Can for example be sulfate ion, chloride ion, acetate ion, nitrate ion, phosphate radical from
Son, formate ion, alkyl sulfonate ion and its mixing etc..
The concentration of each ion in aqueous electrolyte, can be according to application of different electrolyte, solvent and battery etc.
Different situations and be changed allotment.
Preferably, in aqueous electrolyte, the concentration of the first metal ion is 0.1～10mol/L.
Preferably, in aqueous electrolyte, the concentration of the second metal ion is 0.5～15mol/L.
Preferably, in aqueous electrolyte, the concentration of anion is 0.5～12mol/L.
In order that battery performance more optimizes, the pH value range of aqueous electrolyte is 3～7.The scope of pH can be by slow
Electuary is adjusting.The pH of aqueous electrolyte is too high, may affect the concentration of zinc ion in electrolyte, the pH mistakes of aqueous electrolyte
It is low, then can aggravate the corrosion of electrode material.And the pH scopes of electrolyte are maintained at into 3～7, water system electrolysis can be both effectively ensured
The concentration of metal ion in liquid, can also avoid electrode corrosion.
In order to provide more preferable security performance, preferably it is located in the electrolytic solution and between positive pole and negative pole, is additionally provided with barrier film.Every
The short circuit that the both positive and negative polarity that other unexpected factors that film can avoid are caused is connected and causes.
Barrier film does not have particular/special requirement, as long as allow electrolyte pass through and electronic isolation barrier film.Organic system lithium from
The various barrier films that sub- battery is adopted, go for the present invention.Barrier film can also be the other materials such as micropore ceramics dividing plate.
Present invention also offers a kind of set of cells, set of cells includes several above-mentioned batteries, specifically, by series connection,
In parallel or its combination connects two or more battery to produce set of cells.The capacity and voltage of set of cells can be by the series connection of battery
And/or parallel way is freely adjusted.The battery provided according to the present invention or the set of cells built by battery can serve as vehicle
With the power supply of transportation means such as train, and be used as can fix/can install power supply such as uninterrupted power source.
Below by embodiment, the present invention is further described.
Embodiment 1-1
Prepare positive pole：By LiMn2O4 LMO, conductive agent graphite KS15, binding agent butadiene-styrene rubber (SBR) and carboxymethyl cellulose
Sodium (CMC) is according to mass ratio LMO:CMC:SBR:Graphite=86.5:1:2.5:10 mix in water, form uniform positive pole slurry
Material.Plus plate current-collecting body is graphite foil, anode sizing agent is coated on plus plate current-collecting body and forms active material layer, is subsequently carried out
Tabletting, makes positive plate, and positive plate thickness is 0.4mm, and positive active material surface density is 750g/m2。
Prepare negative pole：By zinc active material Zinc Oxide and zinc, conductive agent acetylene black, additive bismuth oxide, Indium sesquioxide., oxidation
Lead and calcium hydroxide, binding agent PTFE and HPMC mixing, are scattered in deionized water, are uniformly mixing to obtain cathode size, will be negative
Pole slurry is coated on the negative current collector punching Copper Foil that aperture is 0.8 millimeter, thickness is 0.2 millimeter, is dried, rolls, is sheared
Obtain porous zinc load piece.Wherein in negative material, the percentage by weight of each component is：Zinc Oxide 80%, zinc 9%, acetylene black
2%th, bismuth oxide 2%, Indium sesquioxide. 1%, lead oxide 0.5%, calcium hydroxide 3%, PTFE2%, HPMC0.5%.
Porous zinc load piece is carried out into tank formation, zinc oxide reduction is made into zinc, specifically, by porous zinc load piece and nickel just
Pole is placed in the potassium hydroxide solution of 6mol/L, with 2.1V constant pressures, 0.2C constant-current charges, is charged to charging capacity and is reached in negative pole
The 150% of Zinc Oxide theoretical capacity, is washed with deionized negative pole to neutrality.
Zinc sulfate, the lithium sulfate of certain mass are weighed, is added to the water dissolving, sulphuric acid zinc concentration is configured to for 2mol/L, sulfur
Electrolyte of the sour lithium concentration for 1mol/L.
Electrolyte is added drop-wise to into barrier film, then positive pole, barrier film, negative electrode layer stacked group are dressed up into battery core, be then charged in housing, group
Dress up battery of the capacity in 250mAh.
Embodiment 1-2
In embodiment 1-2, with embodiment 1-1 the step of prepare positive pole.
Prepare negative pole：By zinc active material zinc, conductive agent acetylene black, additive Indium sesquioxide., lead oxide and calcium hydroxide, glue
Knot agent PTFE and HPMC mixing, is scattered in deionized water, is uniformly mixing to obtain cathode size, cathode size is coated in aperture
, on negative current collector punching Copper Foil that 0.8 millimeter, thickness are 0.2 millimeter, to be dried, rolling, shearing obtain porous zinc load piece.
Wherein in negative material, the percentage by weight of each component is：Zinc 89%, acetylene black 2%, bismuth oxide 2%, Indium sesquioxide. 1%, oxidation
Lead 0.5%, calcium hydroxide 3%, PTFE2%, HPMC0.5%.Porous zinc load piece is not through chemical conversion.
Zinc sulfate, the lithium sulfate of certain mass are weighed, is added to the water dissolving, sulphuric acid zinc concentration is configured to for 2mol/L, sulfur
Electrolyte of the sour lithium concentration for 1mol/L.
Electrolyte is added drop-wise to into barrier film, then positive pole, barrier film, negative electrode layer stacked group are dressed up into battery core, be then charged in housing, group
Dress up battery of the capacity in 250mAh.
Comparative example 1-1
In comparative example 1-1, battery cathode is using the zinc paper tinsel negative pole of 50 μ m-thicks not through chemical conversion.Battery remaining constitute and
Preparation method is with embodiment 1-1.
Performance test
Cycle performance is tested
At 60 DEG C, constant current 100%DOD is carried out with 0.2C multiplying powers to battery in embodiment 1-1～1-2 and comparative example 1-1
Cycle charge-discharge, voltage range are 1.4-2.1V.
Test result is as shown in table 1.
Table 1
| Battery | Discharge capacity/mAh first | Cycle-index |
| Embodiment 1-1 | 267 | 130 |
| Embodiment 1-2 | 265 | 80 |
| Comparative example 1-1 | 258 | 50 |
Table 1 is that discharge capacity and battery capacity drop to the cycle-index of 50% theoretical capacity to battery first.Can by table 1
See, the discharge capacity highest first of the battery containing the porous zinc load obtained through tank formation in embodiment 1-1, next to that real
Apply in a 1-2 not through tank formation but the same battery containing porous zinc load, and directly using zinc paper tinsel as negative pole electricity
Discharge capacity is minimum first in pond；In addition, during high temperature charge and discharge cycles, the discharge capacity of battery in embodiment 1-1
Decay is slow, is dropped in terms of 50% theoretical capacity comes by discharge capacity of the cell, and in embodiment 1-1, battery cycle life is most long, far
More than the cycle life of 50 times of battery in comparative example 1-1.
Battery in above-described embodiment 1-1～1-2 and comparative example 1-1 is disassembled, the dendrite situation of negative terminal surface is observed.
In comparative example 1-1, battery cathode surface has obvious point-like dendrite, and in embodiment 1-1, point-like dendrite needs to examine ability
It was found that, and the point-like dendrite of negative terminal surface is substantially rare than negative terminal surface in comparative example 1-1 in embodiment 1-2.
Embodiment 1-3
Prepare positive pole：By LiMn2O4 LMO, conductive agent graphite KS6, binding agent Kynoar PVDF is according to mass ratio LMO:
KS6:PVDF=86:7:7 mix in water, form uniform anode sizing agent.Plus plate current-collecting body is graphite foil, and anode sizing agent is applied
Overlay on, subsequently carried out tabletting, make positive plate, positive plate thickness is 0.4mm,
Positive active material surface density is 750g/m2。
Prepare negative pole：By zinc active material Zinc Oxide and zinc, binding agent PVAC polyvinylalcohol, polytetrafluoroethylene PTFE mixing,
It is scattered in deionized water, is uniformly mixing to obtain cathode size, it is 0.2 that cathode size is coated in aperture for 0.8 millimeter, thickness
On the negative current collector punching Copper Foil of millimeter, it is dried, rolls, shearing obtains porous zinc load piece.Wherein each group in negative material
Point weight ratio be：Zinc：Zinc Oxide：Polyvinyl alcohol：Politef=83.8：16.2：0.4：4.
Porous zinc load piece is carried out into tank formation, zinc oxide reduction is made into zinc, specifically, by porous zinc load piece and nickel just
Pole is placed in the potassium hydroxide solution of 6mol/L, with 2.1V constant pressures, 0.2C constant-current charges, is charged to charging capacity and is reached in negative pole
The 150% of Zinc Oxide theoretical capacity, is washed with deionized negative pole to neutrality.
Zinc sulfate, the lithium sulfate of certain mass are weighed, is added to the water dissolving, sulphuric acid zinc concentration is configured to for 2mol/L, sulfur
Electrolyte of the sour lithium concentration for 1mol/L.
Electrolyte is added drop-wise to into AGM barrier films, then positive pole, barrier film, negative electrode layer stacked group are dressed up into battery core, be then charged into housing
It is interior, it is assembled into the battery that capacity is 250mAh.
Comparative example 1-2：
In comparative example 1-2, battery cathode is using the zinc paper tinsel negative pole of 50 μ m-thicks not through chemical conversion.Battery remaining constitute and
Preparation method is with embodiment 1-3.
Cycle performance is tested：
By embodiment 1-3 and comparative example 1-2 battery at normal temperatures, under 0.2C multiplying powers, in 1.4V～2.1V voltage ranges
Carry out charge and discharge cycles test.
Test result：
Battery in embodiment 1-3 shows that discharge capacity decay is slow, can run to 300 weeks, the electricity in comparative example 1-2
Pond shows that at 137 weeks unexpected capacity declines problem.
Battery in above-described embodiment 1-3 and comparative example 1-2 is disassembled, the dendrite situation of negative terminal surface is observed.Contrast
In example 1-2, battery cathode surface has obvious point-like dendrite, and in embodiment 1-3, point-like dendrite needs to examine and could send out
It is existing.
To sum up result can draw：Battery containing porous negative pole solves dendrite problems, and the cycle performance of battery is obtained
Improve, and the porous negative pole application obtained through tank formation is in the cells of the present invention, negative pole dendrite problems significantly improve, and follow
The ring life-span is multiplied.
Embodiment 2-1
Prepare positive pole：By LiMn2O4 LMO, conductive agent graphite KS6, binding agent Kynoar PVDF is according to mass ratio LMO:
KS6:PVDF=86:7:7 mix in water, form uniform anode sizing agent.Plus plate current-collecting body is graphite foil, and anode sizing agent is applied
Overlay on, subsequently carried out tabletting, make positive plate, positive plate thickness is 0.4mm,
Positive active material surface density is 750g/m2。
Prepare negative pole：By zinc active material zinc, binding agent Kynoar PVDF, conductive agent activated carbon and graphite powder, point
Dissipate in deionized water, be uniformly mixing to obtain cathode size, it is 0.2 milli that cathode size is coated in aperture for 0.8 millimeter, thickness
On the negative current collector punching Copper Foil of rice, it is dried, rolls, shearing obtains porous zinc load piece.Wherein each component in negative material
Percentage by weight be：Zinc 79%, Kynoar PVDF7%, activated carbon 7%, graphite powder 7%.
Zinc sulfate, the lithium sulfate of certain mass are weighed, is added to the water dissolving, sulphuric acid zinc concentration is configured to for 2mol/L, sulfur
Electrolyte of the sour lithium concentration for 1mol/L.
Electrolyte is added drop-wise to into AGM barrier films, then positive pole, barrier film, negative electrode layer stacked group are dressed up into battery core, be then charged into housing
It is interior, it is assembled into the battery that capacity is 250mA.
Embodiment 2-2
With embodiment 2-1 except that, when preparing negative pole, graphite powder is replaced with CNT, it is each in negative material
The percentage by weight of component is：Zinc 79%, Kynoar PVDF7%, activated carbon 7%, CNT 7%.
Embodiment 2-3
With embodiment 2-1 except that, when preparing negative pole, graphite powder is replaced with Super-P, each group in negative material
Point percentage by weight be：Zinc 79%, Kynoar PVDF7%, activated carbon 7%, Super-P 7%.
Comparative example 2-1
With embodiment 2-1 except that, when preparing negative pole, conductive agent only has activated carbon, each component in negative material
Percentage by weight is：Zinc 79%, Kynoar PVDF 7%, activated carbon 14%.
Cycle performance is tested：
By the battery of embodiment 2-1～2-3 and comparative example 2-1 at normal temperatures, respectively with 0.2C, 1C and 4C multiplying power in 1.4V
Charge and discharge cycles test is carried out in～2.1V voltage ranges.
Test result：
Under 0.2C multiplying powers：Cycle performance of battery in embodiment 2-1～2-2 is better than comparative example 2-1.Specifically, implement
Battery in example 2-1, runs to and unexpected capacity decline occurs within 32 weeks；Battery in embodiment 2-2, runs to and occurs within 30 weeks dashing forward
Right capacity declines；Battery in embodiment 2-3, runs to and unexpected capacity decline occurs within 20 weeks, and it is right that circulating cycle number is all higher than
Battery in ratio 2-1.
Under 1C multiplying powers：Occur when battery in embodiment 2-1～2-3 has been separately operable 125 weeks, 163 weeks and 67 weeks prominent
Right capacity declines, the battery being far later than in comparative example 2-1.
Under 4C multiplying powers：Embodiment 2-1～2-3, the discharge capacity of the cell decay in comparative example 2-1 are slow, in 200 weeks
There is not unexpected capacity to decline.
In general：Under different multiplying, in embodiment 2-1, cathode conductive agent adopts the porous negative pole of graphite and activated carbon
Battery has optimal performance, next to that porous negative electricity of the cathode conductive agent using activated carbon-CNT in embodiment 2-2
Pond.
To sum up show, the battery containing porous negative pole of the present invention can substantially suppress negative pole dendrite problems, it is possible to increase
The cycle performance of battery improves the chemical property of battery on the whole, makes battery be more suitable for practical application.
Although inventor has done elaboration in greater detail and has enumerated to technical scheme, it will be appreciated that for
For those skilled in the art, above-described embodiment is modified and/or flexible or using equivalent replacement scheme is obvious
, can not all depart from the essence of spirit of the present invention, the term occurred in the present invention for the elaboration to technical solution of the present invention and
Understand, can not be construed as limiting the invention.
Claims (15)
1. a kind of battery, including positive pole, negative pole and aqueous electrolyte, the positive pole include positive active material and anode collection
Body；The aqueous electrolyte includes the first metal ion and/or the second metal ion, and first metal ion is in discharge and recharge
In journey the positive pole can it is reversible deviate from-be embedded in, second metal ion is heavy in the cathodic reduction in charging process
Product is the second metal, and second metal oxidation dissolution in discharge process is the second metal ion；It is characterized in that：It is described negative
Pole includes the negative material with loose structure, and the negative material includes zinc active material and negative electrode binder.
2. battery according to claim 1, it is characterised in that：The negative pole is also included with mesh-structured negative pole currect collecting
Body, the negative material are carried on the negative current collector.
3. battery according to claim 2, it is characterised in that：The range of aperture size of the mesh of the negative current collector is
0.3 millimeter -1.5 millimeters, the thickness range of the negative current collector is 0.01 millimeter -0.5 millimeter.
4. battery according to claim 2, it is characterised in that：The zinc active material includes zinc and zinc compound, institute
At least one during zinc compound includes Zinc Oxide, zinc hydroxide and zinc salt is stated, the zinc compound accounts for the negative pole thing
The weight/mass percentage composition of matter is 0-50%.
5. battery according to claim 4, it is characterised in that：The preparation method of the negative pole is comprised the following steps：
Zinc and/or zinc compound are dispersed in water with negative electrode binder, cathode size is uniformly mixing to obtain；By the negative pole
Slurry is coated on the negative current collector, is dried, rolls, is sheared；The zinc load for obtaining and nickel positive pole are placed in into 2-7mol/L
Potassium hydroxide solution in, with 2.1V constant pressures, 0.2C constant-current charges, charge to charging capacity and reach the Zinc Oxide theoretical capacity
100%-150%, wash the zinc load to neutrality.
6. battery according to claim 1, it is characterised in that：The negative electrode binder accounts for the quality hundred of the negative material
Content is divided to be less than 7%.
7. battery according to claim 1, it is characterised in that：The negative electrode binder includes polyvinyl alcohol, hydroxypropyl first
One or more in base cellulose, polyacrylamide, politef, Kynoar.
8. battery according to claim 1, it is characterised in that：The negative material also includes additive, the additive
The weight/mass percentage composition for accounting for the negative material is less than 5%.
9. battery according to claim 8, it is characterised in that：The additive selected from lead, indium, bismuth, the oxide of calcium or
Hydroxide or salt.
10. battery according to claim 1, it is characterised in that：The negative material also includes conductive agent, the conductive agent
The weight/mass percentage composition for accounting for the negative material is less than 5%.
11. batteries according to claim 10, it is characterised in that：The conductive agent is selected from activated carbon, graphite, carbon black, carbon
One or more in nanotube, Graphene and its oxide.
12. batteries according to claim 1, it is characterised in that：The selection of the negative current collector includes copper, lead, is coated with
The copper of lead, indium, bismuth or stannum, ferrum or rustless steel.
13. batteries according to claim 1, it is characterised in that：The pH value of the aqueous electrolyte is 3-7.
A kind of 14. set of cells, including several batteries as described in any one in claim 1-13.
15. a kind of uninterrupted power sources, including the battery as described in any one in claim 1-13.
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| CN2015106081685 | 2015-09-22 | ||
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| CN108336295A (en) * | 2017-12-28 | 2018-07-27 | 广州倬粤动力新能源有限公司 | The preparation method of conductive plate lotion |
| CN108550800A (en) * | 2018-03-28 | 2018-09-18 | 深圳新源柔性科技有限公司 | Composite electrode and battery |
| CN108963241A (en) * | 2017-05-19 | 2018-12-07 | 苏州宝时得电动工具有限公司 | battery, battery pack and uninterruptible power supply |
| CN109103456A (en) * | 2018-06-29 | 2018-12-28 | 浙江工业大学 | A kind of preparation method of the compound porous collector for lithium an- ode protection |
| CN109309191A (en) * | 2017-07-26 | 2019-02-05 | 成都特隆美储能技术有限公司 | A kind of novel long-life energy storage lithium ion battery pole piece and lithium ion battery |
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| CN112271273A (en) * | 2020-10-27 | 2021-01-26 | 佛山市恩力晟和能源科技有限公司 | Zinc electrode for alkaline secondary battery and preparation method thereof |
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| CN112271273A (en) * | 2020-10-27 | 2021-01-26 | 佛山市恩力晟和能源科技有限公司 | Zinc electrode for alkaline secondary battery and preparation method thereof |
| WO2023125523A1 (en) * | 2021-12-28 | 2023-07-06 | 瑞海泊(常州)能源科技有限公司 | Negative electrode material and application thereof |
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Application publication date: 20170329 |