CN103515657B - Battery - Google Patents
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- CN103515657B CN103515657B CN201210208943.4A CN201210208943A CN103515657B CN 103515657 B CN103515657 B CN 103515657B CN 201210208943 A CN201210208943 A CN 201210208943A CN 103515657 B CN103515657 B CN 103515657B
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- electrolyte
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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
-
- 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
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Present invention is disclosed a kind of battery, including positive pole, negative pole and electrolyte, the electrolyte includes electrolyte and can dissolve the electrolyte and make at least one in the aqueous solution or alcoholic solution of electrolyte ionization；The electrolyte also includes making the silica of Electrolyte Gel.Silica can make electrolyte gel, and so, battery of the invention is placed all without leakage anyway, so that cell safety is reliable, last a long time, it is convenient to carry and store.
Description
Technical field
The invention belongs to electrochemical energy storage field, and in particular to a kind of battery.
Background technology
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 automobile, wind energy, solar grid-connected or peak load regulation network, are all badly in need of one
Plant cheap, reliable, the secondary cell of safety and long lifespan.The secondary cell for being developed at present is concentrated mainly on lithium ion battery,
The high temperature sodium-sulphur battery, sodium nickel chlorine battery and vanadium flow battery.These batteries all have respective advantage, such as lithium ion battery and
The high temperature sodium-sulphur battery long lifespan and energy density are high, and vanadium flow battery even more possesses unlimited life-span etc. in theory.But no matter
Which kind of battery, all cannot simultaneously meet cheap, reliable, the requirement of safety and long lifespan.Traditional lithium ion battery is prohibitively expensive,
And have potential safety hazard；The high temperature sodium-sulphur battery manufacturing technology threshold is high, and price is expensive；The multinomial technical bottleneck of vanadium flow battery is current all
Fail to obtain breakthrough etc..
The research of aquo-lithium ion battery is devoted to for this Many researchers, it is desirable to which lithium ion battery is greatly reduced with this
Cost, and propose some with LiMn2O4 as positive pole, oxide such as LiV3O8 of vanadium etc. is negative pole, water is electrolyte
Battery, but the easy leakage of such battery, while not safe enough, also reduce the capacity of battery, so that the life-span is shorter.Separately
Outward, be also inconvenient to carry and store.
The content of the invention
The present invention is intended to provide it is a kind of it is safe and reliable, last a long time, and it is convenient carry and storage battery.
The invention provides a kind of battery, including positive pole, negative pole and electrolyte, the electrolyte includes electrolyte and can
Dissolve the electrolyte and make at least one in the aqueous solution or alcoholic solution of electrolyte ionization；The electrolyte is also wrapped
Including makes the silica of Electrolyte Gel.
Beneficial effects of the present invention：Silica makes electrolyte gel.So, battery place anyway all without
Leakage, so that cell safety is reliable, last a long time, it is convenient to carry and store.
Preferably, the silica is the aerosil prepared by vapor phase method by silicon tetrachloride.
Preferably, the silica is prepared by silicate.
Preferably, the silicate is selected from alumina silicate, sodium metasilicate, potassium silicate, calcium silicates, silicic acid phosphorus, Magnesiumaluminumsilicate, silicic acid
One kind in magnesium lithium.
Preferably, there is silica particle, the particle diameter of the micelle is not more than 20nm after the Electrolyte Gel.
Preferably, the particle diameter of the micelle is located between 10~20nm.
Preferably, the particle diameter of the micelle is located between 5~7nm.
Preferably, there is the micelle first group and particle diameter of the particle diameter between 10~20nm to be located between 5~7nm
Second group.
Preferably, the particle diameter of the micelle is less than 5nm.
Preferably, weight accounting of the silica in the electrolyte is 0.2%~20%.
Preferably, the electrolyte also includes deflocculant, and the deflocculant is selected from polyvinyl alcohol, dextrin, sweet
At least one in oil, polyethylene glycol, polyacrylamide and AEO.
Preferably, the positive pole includes plus plate current-collecting body and participates in the positive active material of electrochemical reaction, the positive pole
Active material can it is reversible deviate from-embedded ion；The negative pole at least includes negative current collector；The electrolyte can be ionized out
There is the active ion of reduction-deposition and oxidation-dissolving, the active ion at least one charge and discharge process in the negative pole
Including metal ion, the metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.
Preferably, the metal ion exists in the form of the mixture of sulfate, acetate or sulfate and acetate
In the electrolyte.
Preferably, the positive active material can it is reversible deviate from-be embedded in lithium ion, sodium ion, zinc ion or magnesium ion.
Specific embodiment
The battery that the present invention is provided is not only safe and reliable and with life-span more long, and very convenient carrying and storage,
In portable type electronic products such as such as mobile phone, notebook computers, electric automobile, electric bicycle, the field such as electric tool has can
The application prospect of sight.
Present invention is disclosed a kind of battery, battery includes positive pole, negative pole and electrolyte, and electrolyte includes electrolyte and can
Dissolve electrolyte and make at least one in the aqueous solution or alcoholic solution of electrolyte ionization；Wherein, electrolyte also includes making electricity
Solve the silica of lyogel.So, electrolyte is made to be in gel state, battery will not produce leakage, so that battery is not only
It is safe and reliable and with longer life, and very convenient carrying and storage.
Silica particle is formed after Electrolyte Gel.The particle diameter of micelle is different, and its specific surface area differs greatly.And micelle
Particle diameter depend primarily on preparation technology.
As shown in table 1, particle diameter is smaller, and the specific surface area of micelle is bigger.Accordingly, the specific surface area of micelle is bigger, micelle
Surface can be just bigger, the reactivity of micelle also accordingly increases.
Table 1
| Particle diameter D (nm) | |
| ＜ 3 | ＞ 1000 |
| 3~4 | 750~900 |
| 7~8 | 350~400 |
| 11~13 | 190~270 |
| 16~20 | 130~170 |
When particle diameter is smaller, it is easy to react to form chemical bond between micelle.When micelle is close to, silicon is passed through between micelle
Alcohol is condensed, and forms silicon oxygen bond, and gel relies primarily on the skeletal support that silicon oxygen bond builds and.Water or alcohol can be wrapped up in skeleton,
So as to form gel.And the process for forming silicon oxygen bond is irreversible so that the skeleton formed by silicon oxygen bond is difficult to be broken.
Therefore, when particle diameter is smaller, quickly, formation gel is fine and close, hard, intensity is big for its gelation rate.
And as the increase of particle diameter, the surface-active of micelle are reduced, micelle centre-to-centre spacing is also gradually increased, mutually reciprocal between particle
The chance that silicon oxygen bond should be formed is reduced.After a small amount of less micelle is coupled to larger micelle, the aggregation rate of particle in system
Will reduce.Now, three-dimensional framework can not be constituted between micelle by forming silicon oxygen bond.
Silica particle surface has many hydroxyls, now can be constituted three-dimensional bone with hydrogen bond formation by Hydrogenbond
Frame.And hydrogen bond is a kind of intermolecular weak binding, it is more easily damaged.Therefore.The skeleton formed by hydrogen bond is easily broken, as long as
Slightly shearing force, skeleton is just destroyed, and the water or alcohol being wrapped in skeleton can just be discharged.But once remove shearing force,
Skeleton structure is set up again, and water or alcohol are wrapped again.In sum, the formation of skeleton and break be entirely it is reversible,
Gels-soft and it is flexible, thixotropy is preferable.
Preferably, the particle diameter of micelle is not more than 20nm.It is three-dimensional although gel cuts dilute property very well if particle size analysis are excessive
Skeleton forms very slow, is not enough to good gelation, and hydration phenomena is also more serious.
Preferably, the particle diameter of micelle is located between 10~20nm.
Preferably, the particle diameter of micelle is not more than 10nm.
Preferably, the particle diameter of micelle is located between 5~7nm.
Preferably, the particle diameter of micelle is located between 3~5nm.
Preferably, micelle has second of first group and particle diameter of the particle diameter between 10~20nm between 5~7nm
Group.Such thickness micelle is reasonably combined, makes gel soft and flexible, and moderate strength, property is coagulated again good.So as to ensure that gel has
While certain toughness, intensity is also moderate.
In addition, the gel electrolyte of superior performance to be obtained, will not only change the size of silica particle, particle is controlled
Surface hydroxyl condensation level, but also to adjust the content of silica.
In electrolyte, silica weight accounting in the electrolytic solution is 0.2%~20%, so as to ensure that electrolyte has
Preferable gelling performance.
Preferably, silica weight accounting in the electrolytic solution is 0.2~0.5%, further improves electrolyte
Gelling performance.
Preferably, silica weight accounting in the electrolytic solution is 1.0~20%, further improves the solidifying of electrolyte
Colloidality energy.
Preferably, silica weight accounting in the electrolytic solution is 1.0~3.2%.
Preferably, silica weight accounting in the electrolytic solution is 4.0~4.5%.
Preferably, silica weight accounting in the electrolytic solution is 5.0~20%.
Preferably, silica is the aerosil prepared by vapor phase method by silicon tetrachloride.
Vapor phase method is called pyrolysismethod, dry method or combustion method.Its raw material is silicon tetrachloride, oxygen and hydrogen, is reacted under high temperature
Form.Reaction equation is：SiCl4+2H2+O2- ＞ SiO2+4HCl.Air and hydrogen respectively through pressurization, separation, cooled dehydrated,
Synthesis hydrolysis stove is sent into after dry, dust removal and filtration.After silicon tetrachloride raw material is delivered into rectifying column rectifying, heated in evaporator and steamed
Hair, and with the air after drying, filtering as carrier, deliver to synthesis hydrolysis stove.It is and a certain amount of after silicon tetrachloride gasifies at high temperature
Hydrogen and oxygen vapor phase hydrolysis are carried out at a high temperature of 1800 DEG C or so；The aerosil for now generating is unbodied ultra-fine
Particle, is cyclic structure, and gel force is strong, surface-active is high, can form the preferable silica gel of thixotropy.
In addition, silica can also be prepared by silicate.In the world, the reserves of silicate are more, are readily obtained, cost ratio
It is relatively low.
Silicate may be selected from sodium metasilicate, alumina silicate, potassium silicate, calcium silicates, silicic acid phosphorus, Magnesiumaluminumsilicate, lithium magnesium silicate
It is a kind of.Certainly, also selected from the montmorillonite with alumina silicate as main component, smectite.
In addition, because water glass solution is cheap, often preparing dioxy with the water glass solution containing sodium metasilicate as raw material
SiClx.Simple process flow is：Water glass solution → acid neutralization → anion-cation exchange resin treatment (stirring) → be evaporated under reduced pressure
Concentration → ultrafiltration.By after ultrafiltration, the purity of silica is higher, the shadow of other metal impurities ion pair battery performances is reduced
Ring, and improve the gelling performance of electrolyte.
In addition, electrolyte also includes deflocculant, to change the configuration of surface of micelle, prevent micelle aggregation and delay glue
The effect of solidifying process, can effectively change the performance of colloid.
Deflocculant may be selected from polyvinyl alcohol, dextrin, glycerine, polyethylene glycol, polyacrylamide and fatty alcohol polyoxy second
At least one in alkene ether.
Preferably, deflocculant is polyacrylamide.Polyacrylamide can effectively alleviate the aquation point of gel electrolyte
Layer.In addition, polyacrylamide can also play a part of to absorb moisture, increase system viscosity, so as to as a kind of viscosity modifier.
Positive pole includes plus plate current-collecting body and participates in the positive active material of electrochemical reaction, and positive active material can be reversible
Abjection-embedded ion；The material of plus plate current-collecting body is selected from the one kind in carbon-based material, metal or alloy；Negative pole at least includes negative
Pole collector；Electrolyte occurs what is reduced-deposit and aoxidize-dissolve in can ionizing out at least one charge and discharge process in negative pole
Active ion.
The carrier that plus plate current-collecting body only conducts and collects as electronics, is not involved in electrochemical reaction, i.e., in battery operated electricity
In the range of pressure, plus plate current-collecting body occurs in being stably present in electrolyte without any side reaction, so as to ensure battery
Cycle performance with stabilization.
Positive active material participates in positive pole 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 is to meet formula Li1+xMnyMzOkCan it is reversible deviate from-be embedded in the spinel structure of lithium ion
Compound, wherein, -1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M be selected from Na, Li, Co, Mg, Ti, Cr,
At least one in V, Zn, Zr, Si, Al.Preferably, positive active material contains LiMn2O4.It is furthermore preferred that positive active material
Contain the LiMn through overdoping or coating modification2O4。
Positive active material is to meet formula Li1+xMyM′zM″cO2+nCan it is reversible deviate from-be embedded in the stratiform knot of lithium ion
The compound of structure, wherein, -1 ＜ x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1, -0.2≤n≤0.2, M, M ', M " is selected respectively
From 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 is to meet formula LixM1-yM′y(XO4)nCan it is reversible deviate from-be embedded in the olivine of lithium ion
The compound of structure, wherein, 0 ＜ x≤2,0≤y≤0.6,1≤n≤1.5, M be selected from Fe, Mn, V or Co, M ' be selected from Mg, Ti,
At least one of Cr, V or Al, X is selected from least one in 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 LiMn2O4Can not represent extensive at present
The formula of " LiMn2O4 " that uses, and should be with formula Li1+xMnyMzOkIt is defined, widely including by various modified
LiMn2O4Positive active material.Likewise, LiFePO4And LiCoO2Also should be construed broadly to include and be mixed by various
What miscellaneous, cladding etc. was modified, 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, can be from such as LiMn2O4、
LiFePO4、LiCoO2、LiMxPO4、LiMxSiOyCompounds such as a kind of (wherein M are variable valency metal).Additionally, can deviate from-it is embedded in sodium
The compound of ion such as NaVPO4F, can deviate from-be embedded in the compound such as γ-MnO of zinc ion2, can deviate from-be embedded in the change of magnesium ion
Compound such as MgMxOy(wherein M is a kind of metal, the ＜ y ＜ 6 of 0.5 ＜ x ＜ 3,2) and with similar functions, can deviate from-be embedded in
The compound of ion or functional group can serve as the positive active material of battery of the present invention.
In a particular embodiment, when preparing anode sizing agent, in addition to positive active material, also need to add conductive agent
And binding agent.
Conductive agent be selected from conducting polymer, activated carbon, Graphene, carbon black, carbon fiber, metallic fiber, metal dust and
One or more in sheet metal.
Binding agent is selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, polyethers, fluorination
One kind in polymer, poly- divinyl polyethylene glycol, polyethyleneglycol diacrylate, glycol dimethacrylates or
The mixture and derivative of above-mentioned polymer.In a specific embodiment, binding agent is selected from polytetrafluoroethylene (PTFE) (PTFE) or poly- inclined
PVF (PVDF).
Negative pole at least includes negative current collector, and specific in the implementation method, negative pole only includes negative current collector, and bears
The carrier that pole collector only conducts and collects as electronics, is not involved in electrochemical reaction.The material of negative current collector is selected from metal
Ni, Cu, Ag, Pb, Mn, Sn, Fe, Al, Zn or by least one in the above-mentioned metal of Passivation Treatment, or elemental silicon, or
Person's carbon-based material, wherein, carbon-based material includes graphite material, such as the paper tinsel of commercialized graphite compacting, wherein shared by graphite
Part by weight scope is 90-100%.The material of negative current collector is also selected from the stainless steel of stainless steel or passivated treatment.
Stainless steel includes but are not limited to stainless (steel) wire and stainless steel foil, likewise, the model of stainless steel can be the stainless of 300 series
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 metal containing hydrogen-evolution overpotential plating/coating high, so as to reduce negative pole pair
The generation of reaction.Plating/coating is selected from the simple substance containing C, Sn, In, Ag, Pb, Co, Zn, at least one in alloy, or oxide
Kind.The thickness range of plating/coating is 1-1000nm.For example：The tin on the negative current collector plated surface of Copper Foil or graphite foil, lead or
Silver.
In addition, alcoholic solution includes but are not limited to ethanol or methyl alcohol.
Electrolyte occurs what is reduced-deposit and aoxidize-dissolve in can ionizing out at least one charge and discharge process in negative pole
Active ion.
Active ion includes metal ion, and metal is selected from least one in Zn, Fe, Cr, Cu, Mn, Ni, Sn.
Metal ion is present in electrolyte in forms such as chlorate, sulfate, nitrate, acetate, formates, phosphate
In.Preferably, metal ion is present in electrolyte in the form of the mixture of sulfate, acetate or sulfate and acetate
In.
Preferably, a kind of electrolyte is also included in electrolyte, electrolyte can be ionized out at least one charge and discharge process
Positive pole can it is reversible deviate from-ion that is embedded in so that the ion-exchange speed in improving positive active material and electrolyte, from
And the high rate charge-discharge performance of the battery in the raising present invention.Specifically, positive active material for can it is reversible deviate from-be embedded in
The compound of lithium ion, electrolyte is corresponding can also to 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 is：Deviate from the ion of reversible abjection-insertion during charging, in positive active material, while
It is oxidized with variable valency metal in positive active material, and ejected electron；Electronics reaches GND via external circuit, while electric
Active ion in solution liquid obtains electronics and is reduced in negative current collector, and is deposited on negative current collector.Discharge process is then
The inverse process of charging.
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 be obvious using equivalent alternative solution
, can not all depart from the essence of spirit of the present invention, the term occurred in the present invention be used for the elaboration of technical solution of the present invention and
Understand, can not be construed as limiting the invention.
Claims (8)
1. a kind of battery, including positive pole, negative pole and electrolyte, the positive pole include plus plate current-collecting body and participate in electrochemical reaction
Positive active material, the positive active material can it is reversible deviate from-embedded ion；The negative pole at least includes negative pole currect collecting
Body；The electrolyte includes electrolyte and can dissolve the electrolyte and make the aqueous solution or alcohol of the electrolyte ionization molten
At least one in liquid；The electrolyte occurs to reduce-sink in can ionizing out at least one charge and discharge process in the negative pole
Product and oxidation-dissolving active ion, the active ion include metal ion, the metal be selected from Zn, Fe, Cr, Cu, Mn,
At least one in Ni, Sn；It is characterized in that：The electrolyte also includes making the silica of Electrolyte Gel, the electrolysis
There is silica particle, there is the micelle first group and particle diameter of the particle diameter between 10~20nm to be located at 5 after lyogel
Second group between~7nm.
2. battery according to claim 1, it is characterised in that：The silica is to pass through gas phase legal system by silicon tetrachloride
Standby aerosil.
3. battery according to claim 1, it is characterised in that：The silica is prepared by silicate.
4. battery according to claim 3, it is characterised in that：The silicate be selected from alumina silicate, sodium metasilicate, potassium silicate,
One kind in calcium silicates, silicic acid phosphorus, Magnesiumaluminumsilicate, lithium magnesium silicate.
5. battery according to claim 1, it is characterised in that：Weight accounting of the silica in the electrolyte
It is 0.2%~20%.
6. battery according to claim 1, it is characterised in that：The electrolyte also includes deflocculant, the colloid
Stabilizer is selected from least in polyvinyl alcohol, dextrin, glycerine, polyethylene glycol, polyacrylamide and AEO
Kind.
7. battery according to claim 1, it is characterised in that：The metal ion is with sulfate, acetate or sulfate
It is present in the electrolyte with the form of the mixture of acetate.
8. battery according to claim 1, 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.
Priority Applications (2)
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| CN201210208943.4A CN103515657B (en) | 2012-06-25 | 2012-06-25 | Battery |
| CN201710381889.6A CN107331905B (en) | 2012-06-25 | 2012-06-25 | Battery with a battery cell |
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| CN201210208943.4A CN103515657B (en) | 2012-06-25 | 2012-06-25 | Battery |
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| CN201710381889.6A Division CN107331905B (en) | 2012-06-25 | 2012-06-25 | Battery with a battery cell |
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| CN103515657A CN103515657A (en) | 2014-01-15 |
| CN103515657B true CN103515657B (en) | 2017-06-27 |
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| CN105336956A (en) * | 2014-06-06 | 2016-02-17 | 苏州宝时得电动工具有限公司 | Battery |
| CN104505533A (en) * | 2015-01-23 | 2015-04-08 | 杭州金色能源科技有限公司 | Gel electrolyte, lithium ion battery and preparation method for lithium ion battery |
| CN106374145A (en) * | 2015-07-21 | 2017-02-01 | 苏州宝时得电动工具有限公司 | Colloidal electrolyte and battery containing colloidal electrolyte |
| CN105932333B (en) * | 2016-06-30 | 2018-09-25 | 普定县银丰农业科技发展有限公司 | A kind of lithium-ion battery electrolytes formula and preparation method |
| TWI628827B (en) * | 2016-12-30 | 2018-07-01 | 財團法人工業技術研究院 | Gel electrolyte and applications thereof |
| CN108461832A (en) * | 2017-02-22 | 2018-08-28 | 中国科学院上海硅酸盐研究所 | A kind of water-system alkali metal ion battery and preparation method thereof based on colloid or gel electrolyte |
| CN110010982A (en) * | 2018-01-05 | 2019-07-12 | 苏州宝时得电动工具有限公司 | Battery |
| CN109585929B (en) * | 2018-10-10 | 2022-03-01 | 湖南立方新能源科技有限责任公司 | Preparation method of silicon cathode lithium ion battery |
| CN111211360B (en) * | 2018-11-22 | 2021-07-06 | 浙江浙能中科储能科技有限公司 | Additive modified aqueous zinc ion 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 |
| CN114388810A (en) * | 2022-01-21 | 2022-04-22 | 戴文韬 | Silicon cathode material and high-capacity quick-charging battery using same |
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| CN1978507A (en) * | 2006-11-24 | 2007-06-13 | 江苏鑫华富能源有限公司 | High-molecular nano polymer electrolyte for lead-acid battery and its compounding method |
| CN102110839A (en) * | 2009-12-29 | 2011-06-29 | 万向电动汽车有限公司 | Battery |
| CN102315413A (en) * | 2011-07-22 | 2012-01-11 | 浙江天能电池(江苏)有限公司 | Explosion-proof valve controlled sealed lead-acid storage battery |
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| CN107331905A (en) | 2017-11-07 |
| CN103515657A (en) | 2014-01-15 |
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