CN105449294A - Battery - Google Patents
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- CN105449294A CN105449294A CN201410502555.6A CN201410502555A CN105449294A CN 105449294 A CN105449294 A CN 105449294A CN 201410502555 A CN201410502555 A CN 201410502555A CN 105449294 A CN105449294 A CN 105449294A
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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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Abstract
The invention provides a battery, which includes an anode, a cathode, and an electrolyte solution. The anode includes a positive active material able to realize reversible separation-embedding of first metal ions. The electrolyte solution consists of first metal ions and second metal ions, in the process of charging and discharging, the first metal ions can achieve reversible separation-embedding at the anode, the second metal ions can be reduced and deposited into second metal and the second metal can be reversibly oxidized and dissolved into second metal ions. Specifically, the anode also includes a composite conductive agent containing carbon nanotubes and acetylene black, the composite conductive agent and the positive active material are in a mass ratio of 0.005-0.3, and the carbon nanotubes and acetylene black are in a mass ratio of 0.25-1.25. The invention can improve the self-discharge problem of batteries, and the provided battery has long cycle life, excellent rate capability and high specific capacity.
Description
Technical field
The invention belongs to electrochemical energy storage field, be specifically related to a kind of battery.
Background technology
In recent years, because economic development and population increase, energy storage and environmental pollution became more and more serious.Therefore, clean, regenerative resource, as solar energy and wind energy, becomes a focus.But the supply of these regenerative resources and demand are along with time and seasonal fluctuation.Therefore, the stability of their power supply should be adjusted by energy storage system, and the change of this energy storage system to supply requirement frequently can have one to respond fast.Up to now, the existing energy, as lead-acid battery or lithium ion battery, is all faced with different challenges or problem.Therefore, be badly in need of high rate capability, safe and reliable energy-storage system and utilize these regenerative resources, comprise contacting and application on electric automobile (EVs) between they and electrical network.Due to high security, high ion conductivity and low cost, in large-scale energy-storage system, water system rechargeable battery has larger advantage than organic rechargeable battery.
Various water system battery, as alkaline Zn-MnO
2battery, lead-acid battery, Ni-MH battery, nickel metal (such as chromium, iron, zinc, cobalt) battery, all commercialization or studied widely.Alkalescence Zn-MnO
2battery is primary cell; Lead-acid battery and Ni-Cd battery are owing to having high toxicity metal, and it causes serious pollution to environment; Ni-MH battery applications rare earth metal and cause its cost very high; The cyclical stability of Ni-Co, Ni-Fe and Ni-Zn battery is poor.The shortcoming of above-mentioned battery hinders their large-scale application in energy-storage system.Recently, metal-ion (the such as Li of many water systems
+, Na
+, K
+and Zn
2+deng) battery caused very large interest based on the metal-ion deintercalation principles of chemistry.Adopt positive electrode (the such as LiMn in organolithium ion battery
2o
4/ VO
2, LiMn
2o
4/ LiV
3o
8, LiMn
2o
4/ TiP
2o
7, LiMn
2o
4/ LiTi
2(PO
4)
3, andLiFePO
4/ LiTi
2(PO
4)
3deng) the existing research of water system " rocking chair " lithium ion battery, but the cycle life of these batteries is all very limited.
In order to the energy storage device of excellent and low cost, a kind of novel aqoue seconary battery is causing to be paid close attention to widely.This battery is based on the reversible deintercalation metal ion of positive pole, and the principle of the reduction metal ions that negative pole is reversible works, as water system Zn/LiMn
2o
4battery.The positive pole LiMn of this battery
2o
4do positive electrode, negative pole is Metal Zn, and electrolyte is the aqueous solution containing zinc ion.The energy storage mechnism of this battery and the different of " rocking chair " battery.At negative pole, zinc electrode is dissolved as Zn rapidly when charging in containing the aqueous solution of zinc ion
2+, Zn during electric discharge
2+reversiblely again be deposited on negative pole.At positive pole, LiMn
2o
4in Li
+deintercalation that can be reversible.A kind of ionic conduction medium is not only by the electrolyte of this battery, or negative pole raw material, and zinc deposition when negative pole is charging is formed, and is consumed again during electric discharge.Due to reversible chemical reaction during this battery charging and discharging, this Zn/LiMn
2o
4battery table reveals high coulombic efficiency.
But, such battery is when charging at present, when anode adopts general carbon containing class conductive agent, conductive agent is easily oxidized thus be consumed, this phenomenon causes self-discharge of battery on the one hand, cause inside battery to produce gas on the other hand, and then affect battery performance, limit the practical application of such battery.
In addition, no matter for organolithium ion battery or this novel water system ion battery, the performance quality of positive electrode all directly can affect the combination property of whole battery system, for the positive active material of reversible deintercalation metal ion, the problem that ubiquity electronics and/or ionic conductivity are not high, this will directly cause the chemical property of battery not ideal enough.For improving the conductivity of its positive electrode, one of Main Means adds conductive agent.Traditional, preparing electrode material is active material, conductive agent and polymeric binder are mixed, but, the improvement DeGrain of general conductive agent (as acetylene black).
Therefore, need to find the conductivity that a kind of suitable conductive agent effectively can not only improve positive electrode active materials, and effectively can suppress self-discharge of battery, thus greatly improve the chemical property of battery.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of battery, improves the conductivity of cell positive material, suppresses self-discharge of battery, improves the chemical property of battery.
For achieving the above object, the technical solution adopted in the present invention is as follows: a kind of battery, comprises positive pole, negative pole and electrolyte, and described positive pole comprises the positive active material can reversiblely deviating from-embed the first metal ion; Described electrolyte comprises the first metal ion and the second metal ion, in charge and discharge process, described first metal ion can be deviate from-embeds positive pole is reversible, and described second metal ion can reduce at negative pole and be deposited as the second metal and the second metal energy reversible oxidation is dissolved as the second metal ion; Described positive pole also comprises the combined conductive agent containing carbon nano-tube and acetylene black, and the mass ratio of described combined conductive agent and positive active material is 0.005-0.3, and the mass ratio of described carbon nano-tube and acetylene black is 0.25-1.25.
Preferably, the mass ratio of described combined conductive agent and positive active material is 0.1-0.3, and the mass ratio of described carbon nano-tube and acetylene black is 0.3-1.
Preferably, described combined conductive agent is three-dimensional network-like structure.
Preferably, the length range of described carbon nano-tube is 50-200 μm, and diameter range is 5-30nm.
Preferably, the granular size scope of described acetylene black is 10-50nm.
Preferably, described positive active material is selected from LiMn
2o
4, LiFePO
4or LiCoO
2in one or more.
Preferably, described first metal ion comprises lithium ion, sodium ion or magnesium ion.
Preferably, described second metal ion is zinc ion.
Preferably, described electrolyte also comprises one or more in sulfate ion, chloride ion, acetate ion, nitrate ion, formate ion and alkyl sulfonate ion.
Preferably, the pH value of described electrolyte is 3-7.
Compared with prior art, the invention has the beneficial effects as follows: the present invention is by adopting the combined conductive agent containing carbon nano-tube and acetylene black, positive active material is made to be dispersed in a kind of conductive network of three-dimensional, increase between active material particle, conductive contacts between conductive agent and active material particle, thus increase the conductivity of positive pole, and combined conductive agent has good stability and antioxygenic property, thus the self discharge of battery is inhibited, high rate performance, specific capacity and cyclical stability all effectively improve.
Accompanying drawing explanation
Below in conjunction with drawings and embodiments, the invention will be further described.
The structural representation of the positive electrode that Fig. 1 provides for embodiment 1;
The SEM figure of the positive electrode that Fig. 2 provides for embodiment 1;
The TEM figure of the positive electrode that Fig. 3 provides for embodiment 1, left figure are the TEM figure observed under low resolution, right figure is the TEM figure observed under high-resolution;
The cyclic voltammetry curve of the battery that Fig. 4 provides for embodiment 1;
1st, 2,3 charging and discharging curve of battery under 4C multiplying power that Fig. 5 provides for embodiment 1;
The charging and discharging curve of battery under different multiplying that Fig. 6 provides for embodiment 1;
The cycle performance figure of battery under different multiplying that Fig. 7 is embodiment 1, comparative example 1 and comparative example 2 provide;
The cycle performance figure of battery under 4C multiplying power that Fig. 8 is embodiment 1, comparative example 1 and comparative example 2 provide;
The charging and discharging curve of battery under 4C multiplying power that Fig. 9 is embodiment 2, comparative example 3 and comparative example 4 provide;
The charging and discharging curve of battery under 1C multiplying power that Figure 10 is embodiment 3, comparative example 5 and comparative example 6 provide;
The ac impedance spectroscopy of battery under 4C multiplying power after 300 circulations that Figure 11 is embodiment 1, comparative example 1 and comparative example 2 provide;
Figure 12 to circulate the XRD figure after 300 times for positive electrode that embodiment 1 provides before charge and discharge cycles and under 4C multiplying power.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Present invention is disclosed a kind of battery, comprise positive pole, negative pole and electrolyte, described positive pole comprises the positive active material can reversiblely deviating from-embed the first metal ion; Described electrolyte comprises the first metal ion and the second metal ion, in charge and discharge process, described first metal ion can be deviate from-embeds positive pole is reversible, and described second metal ion can reduce at negative pole and be deposited as the second metal and the second metal energy reversible oxidation is dissolved as the second metal ion; Described positive pole also comprises the combined conductive agent containing carbon nano-tube and acetylene black, and the mass ratio of described combined conductive agent and positive active material is 0.005-0.3, and the mass ratio of described carbon nano-tube and acetylene black is 0.25-1.25.
The charge-discharge principle of battery of the present invention is: during charging, and positive active material deviates from the first metal ion, simultaneously oxidized with positive active material, and ejected electron; Electronics arrives battery cathode via external circuit, and the second metal ion simultaneously in electrolyte obtains electronics and is reduced on negative pole, and is deposited on negative pole.During electric discharge, the second metal be deposited on negative pole is oxidized, loses electronics and changes the second metal ion into and enter in electrolyte; Electronics arrives positive pole through external circuit, and positive active material accepts electronics and is reduced, and the first metal ion embeds in positive active material simultaneously.
The positive pole of battery comprises positive active material, and positive active material participates in positive pole reaction, and reversiblely can deviate from-embed the first metal ion.
Positive active material can be meet general formula Li
1+xmn
ym
zo
kcan the reversible compound deviating from-embed the spinel structure of lithium ion, wherein ,-1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M is selected from least one in Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al.Preferably, positive active material contains LiMn
2o
4.
Positive active material can be meet general formula Li
1+xm
ym '
zm "
co
2+ncan the reversible compound deviating from-embed the layer structure of lithium ion, wherein,-1<x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1,-0.2≤n≤0.2, M, M ', M " is selected from the middle at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al respectively.Preferably, positive active material contains LiCoO
2.
Positive active material can also be meet general formula Li
xm
1-ym '
y(XO
4)
ncan the reversible compound deviating from-embed the olivine structural of lithium ion, wherein, 0<x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, M ' is selected from the middle at least one of Mg, Ti, Cr, V or Al, and X is selected from least one in S, P or Si.Preferably, positive active material contains LiFePO
4.
In current battery industry, nearly all positive active material all can through overdoping, the modification such as coated.But doping, it is complicated that the means such as coating modification cause the chemical general formula of material to express, as LiMn
2o
4can not represent the general formula of now widely used " LiMn2O4 ", and should with general formula Li
1+xmn
ym
zo
kbe as the criterion, comprise the LiMn through various modification widely
2o
4positive active material.Same, LiFePO
4and LiCoO
2also should be interpreted as widely and comprise through various doping, the modification such as coated, general formula meets Li respectively
xm
1-ym '
y(XO
4)
nand Li
1+xm
ym '
zm "
co
2+npositive active material.
Positive active material is, when reversiblely can deviate from-embed the material of lithium ion, preferably can select as LiMn
2o
4, LiFePO
4, LiCoO
2, LiM
xpO
4, LiM
xsiO
ycompounds such as (wherein M are a kind of variable valency metal).
Preferred, positive active material is LiMn
2o
4.In numerous positive electrode, LiMn
2o
4be considered to one of promising positive electrode of most, cost be low, raw material is sufficient because it has, the advantage such as environmental friendliness, fail safe are good.
In addition, the compound of sodium ion can be deviate from-embed (as NaVPO
4f), the compound of magnesium ion can be deviate from-embed (as MgM
xo
y(wherein M is a kind of metal, 0.5<x<3,2<y<6)) and there is similar functions, can deviate from-compound of embedded ion or functional group can as the positive active material of battery of the present invention.
Positive pole also comprises conductive agent, uses the main purpose of conductive agent to be reduce the resistance of overall positive pole in usual positive pole, strengthens the conductive path between positive electrode particle simultaneously.
In the present invention, conductive agent adopts the combined conductive agent containing carbon nano-tube and acetylene black.
Carbon nano-tube and acetylene black are all the conductive agents that conventional electric conductivity is good.Acetylene black good conductivity, cost is lower, but its conductive path is shorter, easily reunites in charge and discharge process, and electric conductivity can reduce, and acetylene black in aqueous electrolyte when charging Yi Yushui there is oxidation reaction, thus be consumed corrosion, cause the internal resistance of cell to increase.Good and the conductive path path length of carbon nano-tube conductive, but its cost is very high, also very easily reunites in charge and discharge process, electric conductivity also can reduce, and due to the specific area of carbon nano-tube comparatively large, large with the contact area of water in electrolyte, also easily corroded by Water oxidize.
In order to enable the conductive agent in positive electrode take into account conductivity and stability simultaneously, by the burden control of carbon nano-tube in combined conductive agent and acetylene black within the specific limits, make two kinds of conductive agents play synergy, reach better conduction and antioxidant effect.
Concrete, control the mass ratio of carbon nano-tube and acetylene black in combined conductive agent within the scope of 0.25-1.25, preferred, in combined conductive agent, the mass ratio of carbon nano-tube and acetylene black is within the scope of 0.3-1.
On the one hand, the carbon nano-tube of tubulose can form a network-like conductive path, granular acetylene black uniform particles is distributed between conductive network, just the space existed between this conductive network can be coupled together, each for acetylene black particle also can couple together by carbon nanotube conducting network simultaneously, forms continuous, an effective three-dimensional conductive passage.On the other hand, the each particle of acetylene black enters into the network structure that carbon nano-tube is formed, it can be surrounded effectively closely by this network, it is made to avoid the bump contact with electrolyte, reduce the probability that it is oxidized, simultaneously on carbon nano tube network or also can be particles filled by acetylene black between grid, the contact area of carbon nano-tube and electrolyte be greatly reduced, also makes the oxidized probability reduction of carbon nano-tube.By controlling the mixed proportion of carbon nano-tube and acetylene black, make that combined conductive agent is formed effectively, continuous print network configuration, the resistance of overall positive pole can not only be reduced, strengthen the conductive path between positive electrode particle, promote the performance of positive pole, and stability and the antioxygenic property of conductive agent self can be strengthened, improve the overall performance of battery.If the amount of carbon nano-tube is too much in combined conductive agent, then acetylene black can not abundant interconnection network space, and can not fill grid, then conductive effect and antioxidant effect are not good.If the amount of carbon nano-tube is very few, then fully can not form this continuous print three-dimensional net structure, acetylene black particle closely can not be surrounded by conductive network, then conductive effect and antioxidant effect can not reach re-set target.
Therefore, to carbon nano-tube and acetylene black effectively play collaborative to conduct electricity, antioxidation, both ratios must control at preset range.In order to allow combined conductive agent give play to better synergy, the length range of described carbon nano-tube is 50-200 μm, and diameter range is 5-30nm, and the granular size scope of described acetylene black is 10-50nm.
For the positive electrode containing positive active material and conductive agent, conductive network is made to give full play to its effect, the addition of conductive agent and the quality of active material also need to control in suitable scope, now, positive active material particle is surrounded by conductive agent and connects, and conductive agent particle also fills full positive active material void among particles, make fully to contact between conductive agent with positive active material particle.
Concrete, the mass ratio of combined conductive agent and positive active material is 0.005-0.3, and preferably, the mass ratio of combined conductive agent and positive active material is 0.1-0.3.
When positive active material particle is dispersed in the network of combined conductive agent in certain proportion, conductive contacts between each particle increases greatly, electric conductivity will be improved greatly, in addition, positive active material Granular composite is in conductive network, also can reduce the contact area of combined conductive agent and electrolyte further, thus avoid conductive agent oxidized further.If composite conducting agent content is too many, positive active material content in positive pole monomer volume can be caused few, positive active material density reduces, and battery capacity is declined, and increases the contact of conductive agent and electrolyte, causes conductive agent oxidized, and cycle performance reduces; Very little, then in positive active material, electron conduction passage is few for composite conducting agent content, and positive active material can not fully be surrounded by conductive network, causes positive electrode active material utilization not high, and positive electrode capacity reduces, and high rate performance reduces.
Therefore, to ensure under battery system of the present invention that positive electrode has excellent electrical property, positive conductive agent not only will possess excellent electric conductivity, also to possess excellent stability and non-oxidizability, this just requires the ratio by positive active material and combined conductive agent, and in combined conductive agent, the proportional control of carbon nano-tube and acetylene black is in predetermined scope.
Fig. 1 is the structural representation of the network-like structure positive electrode of the three-dimensional that under preferred implementation, combined conductive agent and positive active material are formed.As seen from the figure, because carbon nano-tube has three-dimensional tubular structure, it can form a three-dimensional net structure intersected; Space between network wherein, couples together by acetylene black Granular composite, forms continuous print conductive network; Positive electrode active materials LiMn
2o
4be evenly distributed between this conductive network.This cathode material structure can realize: (1) a kind of conductive channel in long path based on carbon nano-tube and acetylene black associating, to increase LiMn
2o
4between particle, LiMn
2o
4conductive contacts between particle and conductive agent; (2) network configuration interconnected is conducive to electrolyte in interelectrode transmission; (3) acetylene black particle and LiMn
2o
4distribution of particles, fill in a network, and surrounded by network, between three, compact siro spinning technology together, forms a strong composite construction, can realize positive electrode active materials long circulation life.Based on this structural design characteristic, the chemical property of battery will be improved greatly.
Combined conductive agent can be mixed by simple mechanical lapping, and then mix with active material, or directly active material, carbon nano-tube and acetylene black three direct mechanical can be mixed with anode sizing agent, thus obtained positive pole, certainly can also otherwise join in positive pole.
In a particular embodiment, when preparing positive pole, except positive active material and combined conductive agent carbon nano-tube/acetylene black, usually also can add positive electrode binder to promote the performance of positive pole.
Positive electrode binder can be selected from polyethylene oxide, polypropylene oxide, the mixture of a kind of or above-mentioned polymer in polyacrylonitrile, polyimides, polyester, polyethers, fluorinated polymer, poly-divinyl polyethylene glycol, polyethyleneglycol diacrylate, glycol dimethacrylates and derivative.Preferred, positive electrode binder is selected from polytetrafluoroethylene (PTFE), Kynoar (PVDF) or butadiene-styrene rubber (SBR).
Concrete, positive pole also comprises the plus plate current-collecting body of load positive active material, plus plate current-collecting body is only as the carrier of electrical conductivity and collection, do not participate in electrochemical reaction, namely within the scope of battery operating voltage, plus plate current-collecting body can be stable be present in electrolyte and substantially side reaction do not occur, thus ensure that battery has stable cycle performance.
The material of plus plate current-collecting body is selected from the one in carbon-based material, metal or alloy.
Carbon-based material is selected from the one in vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.
Metal comprises Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment.
Alloy comprises stainless steel, carbon steel, Al alloy, Ni alloy, Ti alloy, Cu alloy, Co alloy, Ti-Pt alloy, Pt-Rh alloy or the one in the above-mentioned metal of Passivation Treatment.
Stainless steel comprises stainless (steel) wire, stainless steel foil, and stainless model includes but are not limited to the one in stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.
Preferably, carry out Passivation Treatment to plus plate current-collecting body, its main purpose is, make the surface of plus plate current-collecting body form the oxide-film of one deck passivation, thus in battery charge and discharge process, stable collection and the effect of conduction electron can be played, and cell reaction can not be participated in, ensure that battery performance is stablized.Plus plate current-collecting body deactivating process for the treatment of comprises chemical passivation process or electrochemical passivation process.
Chemical passivation process comprises by oxidizing plus plate current-collecting body, makes anode collection surface form passivating film.The principle that oxidant is selected is that oxidant can make anode collection surface form one deck passivating film and can not dissolve plus plate current-collecting body.Oxidant is selected from but is not limited only to red fuming nitric acid (RFNA) or ceric sulfate (Ce (SO
4)
2).
Electrochemical passivation process comprises and aligns pole collector and carry out electrochemical oxidation or carry out discharge and recharge process to the battery containing plus plate current-collecting body, makes anode collection surface form passivating film.
Be more preferably, positive pole also comprises the composite current collector of load positive active material, and composite current collector comprises plus plate current-collecting body and is coated on the conducting film on plus plate current-collecting body.
Conducting film to meet in aqueous electrolyte can stable existence, be insoluble to electrolyte, do not occur swelling, high voltage can not oxidized, be easy to be processed into densification, the waterproof and requirement of conduction.On the one hand, conducting film can play a protective role to plus plate current-collecting body, avoids aqueous electrolyte to the corrosion of plus plate current-collecting body.On the other hand, be conducive to reducing the contact internal resistance between positive plate and plus plate current-collecting body, improve the energy of battery.
Preferably, the thickness of conducting film is 10 μm ~ 2mm.
Plus plate current-collecting body has the first surface and second that are oppositely arranged, and preferably, the first surface of plus plate current-collecting body and second are all coated with conducting film.
Conducting film comprises the polymer as necessary component, and the weight proportion that polymer accounts for conducting film is 50 ~ 95%, and preferably, polymer is selected from thermoplastic polymer.In order to enable conducting film conduct electricity, there is the form that two kinds feasible: (1) polymer is conducting polymer; (2) except polymer, conducting film also comprises conductive filler.
Conducting polymer choice requirement, namely can not as the ionic conduction of charge transfer medium for having conductive capability but electrochemicaUy inert.Concrete, conducting polymer includes but are not limited to polyacetylene, polypyrrole, polythiophene, polyphenylene sulfide, polyaniline, polyacrylonitrile, poly quinoline, polyparaphenylene (polyparaphenylene) and any mixture thereof.Conducting polymer inherently has conductivity, but can also adulterate to conducting polymer or modification to improve its conductive capability further.Consider from the stable use electric conductivity and battery, the preferred polyaniline of conducting polymer, polypyrrole, polythiophene and polyacetylene.
Same, the choice requirement of conductive filler be surface area little, be difficult to oxidation, degree of crystallinity high, there is conductivity but electrochemicaUy inert, namely can not as the ionic conduction of charge transfer medium.
The material of conductive filler includes but are not limited to conducting polymer, carbon-based material or metal oxide.Conductive filler mass percent scope is in the conductive film 5 ~ 50%.The average grain diameter of conductive filler is not particularly limited, and usual scope is in 100nm ~ 100 μm.
When comprising conductive filler in conducting film, the polymer in conducting film preferably comprises the non-conductive polymer played in conjunction with conductive filler effect, and non-conductive polymer enhances the combination of conductive filler, improves the reliability of battery.Preferably, non-conductive polymer is thermoplastic polymer.
Concrete, thermoplastic polymer includes but are not limited to polyolefin as polyethylene, polypropylene, polybutene, polyvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, one or more in polyether sulfone, butadiene-styrene rubber or Kynoar.Wherein, polyolefin, polyamide and Kynoar is preferably.These polymer are easily melted by heat, and therefore easy and plus plate current-collecting body is combined with each other.In addition, these polymer have large potential window, thus make positive stabilizer pole be also battery output density saving in weight.Preferably, conducting film is attached on plus plate current-collecting body by hot pressing compound, the mode that vacuumizes or spray.
Electrolyte comprises electrolyte and solvent.Wherein, in electrolyte, the object of solvent dissolves electrolyte, and electrolyte is ionized in a solvent, finally generates the cation that can move freely and anion in the electrolytic solution.In the present invention, solvent is preferably the aqueous solution.
Electrolyte comprises the first metal ion and the second metal ion.In charge and discharge process, the first metal ion reversiblely can be deviate from-embeds at positive pole.Namely, when battery charges, the first metal ion is deviate from from positive active material, enters electrolyte; When battery discharge, the first metal ion in electrolyte embeds in positive active material.
Preferably, the first metal ion is selected from lithium ion, sodium ion or magnesium ion.Preferred, the first metal ion is lithium ion.
Second metal ion is deposited as the second metal at cathodic reduction in charging process, and in discharge process, the second burning is dissolved as the second metal ion.Preferably, the second metal ion is zinc ion.
Preferably, the first metal ion is different from the second metal ion.Under a preferred implementation, electrolyte comprises lithium ion and zinc ion.In charge and discharge process, lithium ion embeds at positive pole-deviates from, and zinc ion deposits at negative pole-dissolves.
Anion in electrolyte can be anyly substantially do not affect both positive and negative polarity reaction and the anion that dissolves in a solvent of electrolyte.Can be such as sulfate ion, chloride ion, acetate ion, nitrate ion, phosphate anion, formate ion, alkyl sulfonate ion and mixing thereof etc.
The concentration of each ion in electrolyte, can carry out change allotment according to different situations such as the applications of different electrolyte, solvent and battery.
Preferably, in the electrolytic solution, the concentration of the first metal ion is 0.1 ~ 10mol/L.
Preferably, in the electrolytic solution, the concentration of the second metal ion is 0.5 ~ 15mol/L.
Preferably, in the electrolytic solution, the concentration of anion is 0.5 ~ 12mol/L.
In order to make battery performance more optimize, the pH value range of electrolyte is 3 ~ 7.The scope of pH can be adjusted by buffer.The pH of electrolyte is too high, may affect the concentration of zinc ion in electrolyte, and the pH of electrolyte is too low, then can aggravate the corrosion of electrode material.And the pH scope of electrolyte is remained on 3 ~ 7, both effectively can ensure the concentration of metal ion in electrolyte, can also electrode corrosion be avoided.
Can be there is reversible reduction deposition-oxidation solubilizing reaction in the negative pole of battery, according to the difference of structure and effect, can be divided into again following three kinds of different forms:
In the first preferred embodiment, negative pole only comprises negative current collector, and negative current collector is only as the carrier of electrical conductivity and collection, does not participate in electrochemical reaction.
Material selected from metal Ni, Cu, Ag, Pb, Mn, Sn, Fe, Al of negative current collector or at least one in the above-mentioned metal of Passivation Treatment, or elemental silicon, or carbon-based material; Wherein, carbon-based material comprises graphite material, and the paper tinsel of such as business-like graphite compacting, the part by weight scope wherein shared by graphite is 90 ~ 100%.The material of negative current collector can also be selected from stainless steel or the stainless steel through Passivation Treatment.Stainless steel includes but are not limited to stainless (steel) wire and stainless steel foil, same, and stainless model can be the stainless steel of 300 series, as stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.In addition, negative current collector can also be selected from the metal containing the high plating/coating of hydrogen-evolution overpotential, thus reduces the generation of negative pole side reaction.Plating/coating is selected from the simple substance containing C, Sn, In, Ag, Pb, Co, alloy, or at least one in oxide.The thickness range of plating/coating is 1 ~ 1000nm.Such as: tin on the negative current collector plated surface of Copper Foil or graphite foil, plumbous or silver-colored.
In the second preferred implementation, negative pole, except negative current collector, also comprises the negative electrode active material metal of load on negative current collector.
Preferably, negative electrode active material is metallic zinc.
Wherein, negative current collector with reference to the first preferred implementation, can not repeat them here.
Negative electrode active material is with sheet or Powdered existence.
When adopting the negative electrode active material of sheet, sheet metal and negative current collector form composite bed.
When adopting pulverous negative electrode active material, metal dust being made slurry, then slurry is coated on negative current collector and makes negative pole.In concrete execution mode, when preparing negative pole, except negative electrode active material metal dust, according to actual conditions, also interpolation cathode conductive agent and negative electrode binder promote the performance of negative pole as required.
In the 3rd preferred implementation, directly adopt sheet metal as negative pole, sheet metal, both as negative current collector, is also negative electrode active material simultaneously.
In order to provide better security performance, preferably between positive pole and negative pole, be also provided with barrier film in the electrolytic solution.The short circuit that the both positive and negative polarity that barrier film can avoid other unexpected factors to cause is connected and causes.
Barrier film does not have particular/special requirement, as long as allow electrolyte to pass through and the barrier film of electronic isolation.The various barrier films that organic system lithium ion battery adopts, all go for the present invention.Barrier film can also be the other materials such as micropore ceramics dividing plate.
Below by embodiment, the present invention is further described.
Embodiment 1
Positive electrode active materials LiMn
2o
4employing MTI company.Multi-walled carbon nano-tubes (CNT) chemical vapour deposition technique (CVD) preparation, length can reach 100 μm, and diameter is about 11nm.But in order to prepare pure CNT: with 18%HCl solution and 20% the impurity catalyst of the upper attachment of HF solution removal CNT, then spend deionized water, then drying.
By active material LiMn
2o
4, the combined conductive agent (be denoted as CNT/AB, wherein the mass ratio of CNT and AB is 0.5) containing carbon nano-tube and acetylene black, Kynoar PVDF, 83:10:7 mixes in NMP in mass ratio, and form uniform anode sizing agent, wherein positive electrode is denoted as CNT/AB/LiMn
2o
4, CNT/AB and LiMn
2o
4mass ratio be 0.12.Anode sizing agent is coated in collector graphite foil, air oxygen detrition 24h at 60 DEG C.Above-mentioned obtained positive pole is cut into the round positive plate of diameter 12mm size, the load capacity of active material is 1.5mgcm
-2, and it is under low pressure soaked in the electrolytic solution.Negative pole adopts the circular zinc metal sheet of diameter 12mm to make collector.Barrier film adopts AGM glass fibre.
Electrolyte is the Li comprising 2mol/L
2sO
4with the ZnSO of 1mol/L
4the aqueous solution, record its pH=4 with the LiOH titration of 0.1mol/L.
Above-mentioned obtained positive plate, negative plate, electrolyte and barrier film are assembled into the Swagelok type battery of two electrodes.
Embodiment 2
With embodiment 1 difference be, combined conductive agent CNT/AB and the LiMn of positive electrode
2o
4mass ratio be 0.2, other parts, with embodiment 1, are assembled into battery.
Embodiment 3
That in the combined conductive agent of positive electrode, the mass ratio of CNT and AB is 0.33, and other parts, with embodiment 1, are assembled into battery with embodiment 1 difference.
Comparative example 1
That the conductive agent of positive electrode adopts acetylene black AB, and positive electrode is denoted as AB/LiMn with embodiment 1 difference
2o
4, other parts, with embodiment 1, are assembled into battery.
Comparative example 2
That the conductive agent of positive electrode adopts carbon nano-tube CNT, and positive electrode is denoted as CNT/LiMn with embodiment 1 difference
2o
4, other parts, with embodiment 1, are assembled into battery.
Comparative example 3
With embodiment 1 difference be, combined conductive agent CNT/AB and the LiMn of positive electrode
2o
4mass ratio be 0.05, other parts, with embodiment 1, are assembled into battery.
Comparative example 4
With embodiment 1 difference be, combined conductive agent CNT/AB and the LiMn of positive electrode
2o
4mass ratio be 0.4, other parts, with embodiment 1, are assembled into battery.
Comparative example 5
That in the combined conductive agent of positive electrode, the mass ratio of CNT and AB is 0.2, and other parts, with embodiment 1, are assembled into battery with embodiment 1 difference.
Comparative example 6
That in the combined conductive agent of positive electrode, the mass ratio of CNT and AB is 1.5, and other parts, with embodiment 1, are assembled into battery with embodiment 1 difference.
Material properties test
X ray diffracting spectrum XRD is adopted to observe the crystal structure of the positive electrode that embodiment 1 provides, scanning electron microscope sem and transmission electron microscope tem observation microscopic appearance and size.
Electrochemical property test
Respectively chemical property detection is carried out to the battery that embodiment 1, comparative example 1 and comparative example 2 provide, at room temperature adopt different multiplying (1C=120mAg
-1) in constant current mode, charge-discharge test is carried out to battery, test voltage interval is 1.4-2.1Vvs.Zn
2+/ Zn.At 0.1mVs
-1sweep speed under cyclic voltammetry is carried out to battery, and survey the AC impedance of battery.
SEM figure before the positive electrode circulation that Fig. 2 provides for embodiment 1, Fig. 3 are the TEM figure of this material.As seen from the figure, LiMn
2o
4uniform particles distributes, and CNT and AB forms three-dimensional conductive network, and CNT is interleaving connection between AB and LiMn2O4 particle, and this is conducive to increasing the interfacial contact area between particle.This special network structure can increase LiMn
2o
4between particle, LiMn
2o
4conductive contacts between particle and conductive particle, thus contribute to the chemical property improving battery.
Cyclic voltammetric (CV) curve of the battery that Fig. 4 provides for embodiment 1.As can be seen from the figure, at 0.1mVs
-1sweep speed under, CV curve has two pairs of redox peaks, is in 1.82/1.78V and 1.96/1.92V place respectively.The Li of spinel structure positive electrode in this result and water system battery
+deintercalation is consistent.Oxidation peak is caused by the electrode polarization in cyclic process with the peak-to-peak potential difference of reduction, polarization makes oxidation peak voltage move to positive potential, and reduction peak voltage moves to negative potential, but, oxidation peak only has 0.04V with the peak-to-peak potential difference of reduction, therefore can think Li
+deintercalation be reversible.And the peak shape at redox peak almost overlaps in 3 cyclic processes, this also proves that combined conductive agent CNT/AB network configuration is very stable in this system, and CNT/AB is good conductivity not only, and non-oxidizability is also fine, and these are all conducive to LiMn
2o
4excellent cycle performance and high rate performance are given play to.
1st, 2,3 charging and discharging curve of battery under 4C multiplying power that Fig. 5 provides for embodiment 1.Every bar curve there are two voltage platforms clearly, show LiMn
2o
4middle Li
+deintercalation be a two-phase process, this is consistent with the result of above-mentioned CV curve.The initial charge/discharge specific capacity of this battery is respectively 146 and 139mAhg
-1, coulombic efficiency is 95.2% first, more much higher than the coulombic efficiency first of organolithium ion secondary battery, this is because can not form SEI film in water system battery.In addition, the high specific discharge capacity of battery also shows to have three-dimensional long conductive path based on CNT and AB, constitutes the network configuration connected that crosses one another, thus is conducive to LiMn
2o
4its performance of better performance.
The charging and discharging curve of battery under different multiplying (1C, 4C, 10C, 20C) that Fig. 6 provides for embodiment 1.As we know from the figure, the charge and discharge voltage platform of the battery of embodiment 1 appears near 1.95V and 1.80V respectively, and along with the increase of multiplying power, although the polarization of charging and discharging curve is large in change, polarization is not very serious, and under 20C multiplying power, battery still has 70mAhg
-1the specific discharge capacity of left and right.The above results shows, the positive electrode with combined conductive agent shows good invertibity, and this is also consistent with the result of CV curve.
The cycle performance figure of battery under different multiplying that Fig. 7 is embodiment 1, comparative example 1 and comparative example 2 provide.As can be seen from the figure, no matter under large multiplying power or little multiplying power, the specific discharge capacity with the battery of combined conductive agent CNT/AB is higher than the specific capacity of the battery with single conductive agent AB or CNT.Time under 10C multiplying power, the specific discharge capacity of the battery of embodiment 1 still can reach 105mAhg
-1, and when battery circulates after 30 times under 1C, 4C, 10C, under 4C, carry out charge and discharge cycles again, the capacity before specific capacity still can reach under 4C multiplying power, namely capability retention is about 100%.
The cycle performance figure of battery under 4C multiplying power that Fig. 8 is embodiment 1, comparative example 1 and comparative example 2 provide.After 300 circulations, the battery that embodiment 1 provides still has 92mAhg
-1specific discharge capacity, higher than the specific discharge capacity (64mAhg of the battery that comparative example 1 or comparative example 2 provide
-1, 84mAhg
-1), and the coulombic efficiency of battery keeps stable in cyclic process, nearly all reaches 100%.These results show to adopt the battery of combined conductive agent to have excellent cyclical stability and invertibity, CNT or AB that the structural rate formed after proving CNT and AB compound is single is stable a lot, and conductivity is also fine.Single conductive agent CNT or AB easily oxidized corrosion in charge and discharge process, also easily reunites under high current density.
The charging and discharging curve of battery under 4C multiplying power that Fig. 9 is embodiment 2, comparative example 3 and comparative example 4 provide.As seen from the figure, the specific capacity of the battery that embodiment 2 provides is apparently higher than the battery of comparative example 3 with comparative example 4, and the polarization of the battery of embodiment 2 is minimum.Indicate when the combined conductive agent CNT/AB in positive electrode is different from the proportioning of positive active material, the performance of positive electrode also can be different, and the too much or very few positive electrode that all can not make of the content of combined conductive agent CNT/AB shows excellent performance.The charging and discharging curve of battery under 1C multiplying power that Figure 10 is embodiment 3, comparative example 5 and comparative example 6 provide.As seen from the figure, the specific capacity of the battery that embodiment 3 provides is apparently higher than the battery of comparative example 5 with comparative example 6, and the polarization of the battery of embodiment 3 is minimum.Similar with the result of Fig. 9, when the proportioning of CNT and the AB in positive electrode combined conductive agent is different, the performance of positive electrode also can be different, the excessive or too small performance that positive electrode all can not be made to show excellence of the mass ratio of combined conductive agent CNT and AB.
The above results shows, after conductive agent CNT and AB compound, conductive effect and antioxygenic property all improve a lot than single conductive agent CNT or AB, but not the compound of arbitrary proportion can make positive active material give play to excellent performance, only has CNT, AB and LiMn
2o
4amount when controlling within the scope of certain proportion, combined conductive agent CNT/AB just has excellent conductivity and non-oxidizability, thus ensures positive active material LiMn
2o
4excellent high rate performance and cycle performance are given play to.This is because only have the ratio controlling three, CNT, AB could form effective interconnection, closely surround mutually the network configuration combined, LiMn
2o
4particle also can distribute uniformly, be filled in this network, makes this network not only have strong, stable structure, not easily oxidized, also effectively can improve ion and the electron conduction of positive active material simultaneously.
The ac impedance spectroscopy of battery under 4C multiplying power after 300 circulations that Figure 11 is embodiment 1, comparative example 1 and comparative example 2 provide.As can be seen from the figure, two semicircles of ac impedance spectroscopy by medium, high frequency and the rectilinear(-al) at low frequency place.Be with the difference of the ac impedance spectroscopy of organolithium ion battery, the representative of the semicircle of aquo-lithium ion battery high frequency treatment be contact impedance, and do not represent SEI membrane impedance.Two semicircles on the battery impedance collection of illustrative plates of embodiment 1 are all less than the semicircle of comparative example example 1, comparative example 2, illustrate by by after conductive agent CNT and AB compound, LiMn
2o
4contact impedance and Charge-transfer resistance be reduced, this also demonstrates CNT/AB three-dimensional conductive network configuration can accelerate LiMn
2o
4the transmission speed of middle electronics and ion, thus improve LiMn
2o
4performance.
The positive electrode CNT/AB/LiMn that Figure 12 provides for embodiment 1
2o
4circulate the figure of the XRD after 300 times before charge and discharge cycles and under 4C multiplying power.Curves before curve after charge and discharge cycles 300 times and non-charge and discharge, illustrates the LiMn with combined conductive agent
2o
4the Stability Analysis of Structures of material, its long circulation life is good.
Although inventor has done more detailed elaboration to technical scheme of the present invention and has enumerated, be to be understood that, to those skilled in the art, above-described embodiment to be modified and/or flexible or adopt equivalent replacement scheme to be obvious, all can not depart from the essence of spirit of the present invention, the term occurred in the present invention, for the elaboration of technical solution of the present invention and understanding, can not be construed as limiting the invention.
Claims (10)
1. a battery, comprises positive pole, negative pole and electrolyte, and described positive pole comprises the positive active material can reversiblely deviating from-embed the first metal ion; Described electrolyte comprises the first metal ion and the second metal ion, in charge and discharge process, described first metal ion can be deviate from-embeds positive pole is reversible, and described second metal ion can reduce at negative pole and be deposited as the second metal and the second metal energy reversible oxidation is dissolved as the second metal ion; It is characterized in that: described positive pole also comprises the combined conductive agent containing carbon nano-tube and acetylene black, the mass ratio of described combined conductive agent and positive active material is 0.005-0.3, and the mass ratio of described carbon nano-tube and acetylene black is 0.25-1.25.
2. battery according to claim 1, is characterized in that: the mass ratio of described combined conductive agent and positive active material is 0.1-0.3, and the mass ratio of described carbon nano-tube and acetylene black is 0.3-1.
3. battery according to claim 1, is characterized in that: described combined conductive agent is three-dimensional network-like structure.
4. battery according to claim 1, is characterized in that: the length range of described carbon nano-tube is 50-200 μm, and diameter range is 5-30nm.
5. battery according to claim 1, is characterized in that: the granular size scope of described acetylene black is 10-50nm.
6. battery according to claim 1, is characterized in that: described positive active material is selected from LiMn
2o
4, LiFePO
4or LiCoO
2in one or more.
7. battery according to claim 1, is characterized in that: described first metal ion comprises lithium ion, sodium ion or magnesium ion.
8. battery according to claim 1, is characterized in that: described second metal ion is zinc ion.
9. battery according to claim 1, is characterized in that: described electrolyte also comprises one or more in sulfate ion, chloride ion, acetate ion, nitrate ion, formate ion and alkyl sulfonate ion.
10. battery according to claim 1, is characterized in that: the pH value of described electrolyte is 3-7.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410502555.6A CN105449294A (en) | 2014-09-26 | 2014-09-26 | Battery |
| EP15843519.8A EP3200265A4 (en) | 2014-09-26 | 2015-09-25 | Battery, battery pack and continuous power supply |
| PCT/CN2015/090769 WO2016045622A1 (en) | 2014-09-26 | 2015-09-25 | Battery, battery pack and continuous power supply |
| US15/513,640 US11069891B2 (en) | 2014-09-26 | 2015-09-25 | Battery, battery pack and continuous power supply |
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|---|---|---|---|
| CN201410502555.6A CN105449294A (en) | 2014-09-26 | 2014-09-26 | Battery |
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| CN105449294A true CN105449294A (en) | 2016-03-30 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107046152A (en) * | 2016-11-11 | 2017-08-15 | 中广核工程有限公司 | Used in nuclear power station lead-acid accumulator and its positive pole anti-corrosion method |
| CN107302107A (en) * | 2016-04-15 | 2017-10-27 | 苏州宝时得电动工具有限公司 | electrolyte, battery and battery pack |
| CN108063253A (en) * | 2016-11-07 | 2018-05-22 | 苏州宝时得电动工具有限公司 | Graphene and preparation method thereof, the Anode and battery containing graphene |
| CN111211255A (en) * | 2020-01-07 | 2020-05-29 | 北京科技大学 | Water-based lithium titanate battery and preparation method thereof |
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| CN1770515A (en) * | 2005-08-22 | 2006-05-10 | 中国科学院成都有机化学有限公司 | Anode, cathode material conductive agent for lithium-ion secondary battery and preparation method thereof |
| CN103107373A (en) * | 2011-11-14 | 2013-05-15 | 苏州宝时得电动工具有限公司 | Battery |
| CN103560248A (en) * | 2013-09-27 | 2014-02-05 | 清华大学深圳研究生院 | Graphene based composite conductive agent, its preparation method and application in lithium ion battery |
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| CN1770515A (en) * | 2005-08-22 | 2006-05-10 | 中国科学院成都有机化学有限公司 | Anode, cathode material conductive agent for lithium-ion secondary battery and preparation method thereof |
| CN103107373A (en) * | 2011-11-14 | 2013-05-15 | 苏州宝时得电动工具有限公司 | Battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107302107A (en) * | 2016-04-15 | 2017-10-27 | 苏州宝时得电动工具有限公司 | electrolyte, battery and battery pack |
| CN108063253A (en) * | 2016-11-07 | 2018-05-22 | 苏州宝时得电动工具有限公司 | Graphene and preparation method thereof, the Anode and battery containing graphene |
| CN107046152A (en) * | 2016-11-11 | 2017-08-15 | 中广核工程有限公司 | Used in nuclear power station lead-acid accumulator and its positive pole anti-corrosion method |
| CN111211255A (en) * | 2020-01-07 | 2020-05-29 | 北京科技大学 | Water-based lithium titanate battery and preparation method thereof |
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Application publication date: 20160330 |