CN105742637A - Positive material and battery containing same - Google Patents
Positive material and battery containing same Download PDFInfo
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- CN105742637A CN105742637A CN201410765967.9A CN201410765967A CN105742637A CN 105742637 A CN105742637 A CN 105742637A CN 201410765967 A CN201410765967 A CN 201410765967A CN 105742637 A CN105742637 A CN 105742637A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a positive material. The positive material comprises a positive active material and a positive conductive agent, wherein a tin antimony oxide is doped into the positive conductive agent; and the tin antimony oxide accounts for 0.5%-1% of mass fraction of the positive conductive agent. The invention further discloses a battery. The battery comprises a positive electrode, a negative electrode and an electrolyte; and the positive electrode comprises the positive material. The tin antimony oxide has good stability and corrosion resistance; self-discharge of the battery is reduced; and the cycle performance of the battery is strengthened.
Description
Technical field
The present invention relates to a kind of positive electrode.
The invention still further relates to a kind of battery.
Background technology
Lead-acid battery, its appearance is super century-old, has the battery technology of maturation, in occupation of the absolute market share in the energy storage fields such as automobile starting storage battery, electric bicycle, UPS.Although lead-acid battery service life cycle is relatively low, energy density is relatively low, but it is very cheap to have price, the advantage that cost performance is very high.Therefore, in the last few years, Ni-MH battery, lithium ion battery, sodium-sulphur battery etc., lead-acid battery all cannot be replaced in energy storage field.
Newly occur in that a kind of water system battery.The operation principle of this battery is, positive pole deviates from-insertion reaction based on the first metal ion, negative pole is based on the deposition-dissolving reaction of the second metal ion, and electrolyte deviates from-the first metal ion of insertion reaction and participate in the second metal ion that cathode deposition-dissolvings is reacted containing participating in positive pole.The theoretical energy density of the type battery is 160Wh/Kg, it is contemplated that actual energy density is up to 50～80Wh/Kg.In sum, the type battery promises to be the energy-storage battery of future generation substituting lead-acid battery very much, has great commercial value.
But, this battery is when charging at present, and anode conductive agent graphite can occur corrosion thus being consumed, and this phenomenon causes that self-discharge of battery is serious on the one hand, causes inside battery to produce gas on the other hand, and then makes the cycle life of battery reduce rapidly.
Summary of the invention
The technical problem to be solved is to provide a kind of positive electrode that can reduce positive conductive agent corrosion, thus reducing the self discharge of battery.
The invention provides a kind of positive electrode, described positive electrode includes positive active material and positive conductive agent, it is characterized in that, doped with tin-antiomony oxide in described positive conductive agent, described tin-antiomony oxide accounts for the mass fraction of described positive conductive agent and ranges for 0.5%～1%.
Preferably, described positive conductive agent includes the one in graphite KS15, graphite SFG or two kinds.
Compared with prior art, by doped stannum oxide antimony in positive conductive agent, the positive conductive agent of the present invention can well take into account electric conductivity and stability, it is to avoid conductive agent is subject to the corrosion of electrolyte
Present invention also offers a kind of battery, described battery includes positive pole, negative pole and is arranged on the electrolyte between described positive pole and negative pole, and described positive pole includes plus plate current-collecting body and positive electrode, and described electrolyte includes electrolyte and aqueous solution；Described electrolyte at least can ionize out the first metal ion and the second metal ion；Described first metal ion reversible can be deviate from-embed at described positive pole in charge and discharge process；Described second metal ion is deposited as the second metal at described cathodic reduction in charging process, and described second metal oxidation dissolution in discharge process is the second metal ion；Described positive electrode is above-mentioned positive electrode.
Preferably, the pH value of described electrolyte is 3～7.
Preferably, described solvent is water or the mixture of alcohol or water and alcohol.
Preferably, described first metal ion one in lithium ion, sodium ion, magnesium ion and zinc ion.
Preferably, described second metal ion is selected from manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion.
Preferably, described electrolyte also includes sulfate ion, chloride ion, acetate ion, nitrate ion, formate ion and one or more in alkyl sulfonate ion.
Preferably, described plus plate current-collecting body is graphite foil.
Compared with prior art, the present invention is by doped stannum oxide antimony in positive conductive agent so that positive conductive agent can well take into account electric conductivity and stability, it is to avoid conductive agent is subject to the corrosion of electrolyte, reduce the self discharge of battery, finally enhance the performance of battery.
Detailed description of the invention
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 is only in order to explain the present invention, is not intended to limit the present invention.
In one embodiment, the present invention proposes a kind of positive electrode, and it includes positive active material and positive conductive agent.Doped with tin-antiomony oxide in positive conductive agent, described tin-antiomony oxide accounts for the mass fraction of described positive conductive agent and ranges for 0.5%～1%.Doping process is positive conductive agent and tin-antiomony oxide physical mixed.Preferably, doping process also includes grinding.
The purpose using positive conductive agent in positive pole is to reduce the resistance of overall positive pole, strengthens the conductive path between positive electrode granule simultaneously.Preferably, positive conductive agent adopts the one in graphite KS15, graphite SFG or two kinds.
For strengthening the resistance to corrosion of positive conductive agent, doped with tin-antiomony oxide in positive conductive agent.Tin-antiomony oxide, is again nanometer antimony-doped stannic oxide, antimony tin oxide, is called for short ATO (AntimonyTinOxide).Tin-antiomony oxide has good corrosion resistance, and it is made up of a nanometer ultramicron metal oxide powder for chemical stabilization, and to heat, the physical property change that the external environment condition such as humidity causes is little.In the present embodiment, positive conductive agent doped stannum oxide antimony, improve the overpotential for oxygen evolution of positive pole, slow down the oxidational losses of positive conductive agent, thus reducing self discharge.Tin-antiomony oxide accounts for the mass ratio of positive conductive agent and ranges for 0.5%～1%.Preferably, tin-antiomony oxide accounts for the mass ratio of positive conductive agent is 0.5%.If tin-antiomony oxide accounts for the mass ratio of positive conductive agent more than 1%, battery will be produced negative effect.
In the present embodiment, being also added with binding agent in positive electrode, binding agent is conducive to making positive active material and conductive agent be bonded together uniformly.Concrete, binding agent is selected from but is not limited only to polymer, polymer at least one in politef (PTFE), Kynoar (PVDF), sodium carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose derivant (CMCderivation), butadiene-styrene rubber (SBR), butadiene-styrene rubber derivant (SBRderivation).Butadiene-styrene rubber derivant has hydrophilic butadiene-styrene rubber (PSBR100) such as what obtained by chemical modification.
In another embodiment, present invention also offers a kind of battery, including positive pole, negative pole and electrolyte.Positive pole includes plus plate current-collecting body and positive electrode, and electrolyte includes electrolyte and aqueous solution；Electrolyte at least can ionize out the first metal ion and the second metal ion；First metal ion reversible can be deviate from-embed at described positive pole in charge and discharge process；Second metal ion is deposited as the second metal at described cathodic reduction in charging process, and the second metal oxidation dissolution in discharge process is the second metal ion；Positive electrode includes positive active material and positive conductive agent, doped with tin-antiomony oxide in positive conductive agent.
In positive electrode, positive conductive agent, just no longer repeats at preceding detailed description here one by one doped with tin-antiomony oxide.
Preferably, positive active material has spinel structure, layer structure or olivine structural.
Preferably, first metal ion one in lithium ion, sodium ion and magnesium ion, corresponding, positive active material reversible can deviate from-embed lithium ion, sodium ion or magnesium ion.
In a preferred embodiment, positive active material can be consistent with formula Li1+xMnyMzOkThe compound of the spinel structure that reversible can deviate from-embed lithium ion, wherein ,-1≤x≤0.5,1≤y≤2.5,0≤z≤0.5,3≤k≤6, M at least one in Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si, Al, Ni.Preferably, positive active material contains LiMn2O4.It is furthermore preferred that positive active material contains the LiMn through overdoping or coating modification2O4。
Positive active material can be consistent with formula Li1+xMyM′zM″cO2+nThe compound of the layer structure that reversible can deviate from-embed lithium ion, wherein ,-1 < x≤0.5,0≤y≤1,0≤z≤1,0≤c≤1 ,-0.2≤n≤0.2, M, M ', M " are respectively selected from the middle at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si or Al.Preferably, positive active material contains LiCoO2。
Positive active material can be consistent with formula LixM1-yM′y(XO4)nThe compound of the olivine structural that reversible can deviate from-embed lithium ion, wherein, 0 < x≤2,0≤y≤0.6,1≤n≤1.5, M is selected from Fe, Mn, V or Co, and M ' is selected from the middle at least one of Mg, Ti, Cr, V or Al, X at 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 through the modification such as overdoping, cladding.But doping, the means such as coating modification cause the chemical general formula of material to express complexity, such as LiMn2O4Can not represent the formula of now widely used " LiMn2O4 ", and should with formula Li1+xMnyMzOkIt is as the criterion, includes widely through various modified LiMn2O4Positive active material.Same, LiFePO4And LiCoO2Also should being construed broadly to include modified through various doping, cladding etc., formula corresponds with LixM1-yM′y(XO4)nAnd Li1+xMyM′zM″cO2+nPositive active material.
Positive active material be lithium ion deviate from-intercalation compound time, it is possible to select such as LiMn2O4、LiFePO4、LiCoO2、LiMxPO4、LiMxSiOyCompounds such as (wherein M are a kind of variable valency metal).
Additionally, the compound N aVPO of sodium ion can be deviate from-embed4F, can deviate from-embed the compound Mg M of magnesium ionxOy(wherein M is a kind of metal, 0.5 < x < 3,2 < y < 6) and there is similar functions, it is possible to deviate from-compound of embedded ion or functional group can serve as the positive active material of battery of the present invention, therefore, the invention is not limited in lithium ion battery.
Positive pole also includes the plus plate current-collecting body of load positive active material, plus plate current-collecting body is only used as electronics conduction and the carrier collected, it is not involved in electrochemical reaction, namely within the scope of battery operating voltage, plus plate current-collecting body can be stable be present in electrolyte and side reaction do not occur substantially, thus ensureing that battery has stable cycle performance.
The material of plus plate current-collecting body one in carbon-based material, metal and alloy.
Carbon-based material one in vitreous carbon, graphite foil, graphite flake, foamy carbon, carbon felt, carbon cloth, carbon fiber.In a particular embodiment, plus plate current-collecting body is graphite, and such as the paper tinsel that business-like graphite is suppressed, wherein the part by weight shared by graphite ranges for 90-100%.
Preferably, plus plate current-collecting body is graphite foil.Preferably, graphite foil and being combined into of positive electrode are bondd by conducting resinl.
Metal includes Ni, Al, Fe, Cu, Pb, Ti, Cr, Mo, Co, Ag or the one in the above-mentioned metal of Passivation Treatment.
Alloy includes rustless 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.
Rustless steel includes 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, being passivated plus plate current-collecting body processing, its main purpose is, the surface making plus plate current-collecting body forms the oxide-film of one layer of passivation, thus in battery charge and discharge process, can play stable collection and the effect of conduction electronics, without participating 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 electrochemical passivation processes.
Chemical passivation processes and includes by oxidizing plus plate current-collecting body, makes anode collection surface form passivating film.The principle that oxidant selects is that oxidant can make anode collection surface form one layer of passivating film without dissolving plus plate current-collecting body.Oxidant is selected from but is not limited only to concentrated nitric acid or ceric sulfate (Ce (SO4)2)。
Electrochemical passivation processes and includes plus plate current-collecting body carrying out electrochemical oxidation or the battery containing plus plate current-collecting body being carried out discharge and recharge process, makes anode collection surface form passivating film.
More preferably, positive pole also includes the composite current collector of load positive active material, and composite current collector includes plus plate current-collecting body and is coated on plus plate current-collecting body upper conductive film.
The selection of conducting film in aqueous electrolyte can stable existence, insoluble in electrolyte, do not occur swelling, high voltage can not oxidized, be easily processed into densification, the waterproof and film that conducts electricity.On the one hand, plus plate current-collecting body can be played a protective role by conducting film, it is to avoid the aqueous electrolyte corrosion to plus plate current-collecting body.On the other hand, advantageously reduce the internal resistance that contacts between positive plate with plus plate current-collecting body, improve the energy of battery.
Preferably, the thickness of conducting film is 10 μm of-2mm, and conducting film can not only effectively play the effect of protection plus plate current-collecting body, and advantageously reduces the internal resistance that contacts between positive active material with plus plate current-collecting body, improves the energy of battery.
Plus plate current-collecting body has first and second being oppositely arranged, it is preferred that first of plus plate current-collecting body and second is all coated with conducting film.
Conducting film comprises the polymer as necessary component, and it is 50-95% that polymer accounts for the weight proportion of conducting film, it is preferred that polymer is selected from thermoplastic polymer.In order to enable conducting film to conduct electricity, there is form two kinds feasible: (1) polymer is conducting polymer；(2) except polymer, conducting film also comprises conductive filler.
Conducting polymer choice requirement, namely will 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 electric conductivity, it is also possible to conducting polymer is adulterated or modified to improve its conductive capability further.Stable use from electric conductivity and battery is considered, the preferred polyaniline of conducting polymer, polypyrrole, polythiophene and polyacetylene.
Same, the choice requirement of conductive filler is that surface area is little, be difficult to aoxidize, degree of crystallinity is high, have electric conductivity but electrochemicaUy inert, namely will 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 in the conductive film ranges for 5-50%.The mean diameter of conductive filler is not particularly limited, and usual scope is at 100nm to 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 such as polyethylene, polypropylene, polybutene, polrvinyl chloride, polystyrene, polyamide, Merlon, polymethyl methacrylate, polyformaldehyde, polyphenylene oxide, polysulfones, one or more in polyether sulfone, butadiene-styrene rubber or Kynoar.Wherein, it is preferred to polyolefin, polyamide and Kynoar.These polymer melt easily by heat, are therefore easily combined with each other with plus plate current-collecting body.Additionally, these polymer have big potential window, so that positive stabilizer pole for battery output density saving weight.
Preferably, conducting film is attached on plus plate current-collecting body by the mode of hot pressing compound, evacuation or spraying.
Hereinafter, the electrolyte of the present invention is described in detail and illustrates.
In the electrolyte of battery, the purpose of solvent is to dissolve electrolyte, and makes electrolyte ionize in a solvent, finally generates the cation that can move freely and anion in the electrolytic solution.
Solvent is preferably the mixture of water or alcohol or water and alcohol.Wherein alcohol includes but not limited to methanol or ethanol.
Electrolyte includes the first metal ion and the second metal ion, wherein, the first metal ion in electrolyte, reversible can deviate from-embed at positive pole in charge and discharge process.Namely, when battery discharge, the first metal ion in electrolyte embeds in positive active material；When battery charges, the first metal ion is deviate from from positive active material, enters electrolyte.
Preferably, the first metal ion is selected from lithium ion or sodium ion, more preferably lithium ion.
The second metal ion in electrolyte, can reduce at negative pole in charge and discharge process and be deposited as the second metal and the dissolving of the second metal energy reversible oxidation.Namely, when battery charges, the second reducing metal ions in electrolyte becomes the second metal, is deposited on negative pole；When battery discharge, the second metal oxygen is melted into the second metal ion and dissolves from negative pole, enters electrolyte.
Preferably, the second metal ion is selected from manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion；It is more preferably zinc ion.
Under a preferred embodiment, first metal ion of the present invention is selected from lithium ion, and the second metal ion is selected from zinc ion simultaneously, and namely electrolyte cationic is lithium ion and zinc ion.
Anion in electrolyte, it is possible to be any anion having substantially no effect on both positive and negative polarity reaction and electrolyte dissolving in a solvent.Can be such as sulfate ion, chloride ion, acetate ion, formate ion, phosphate anion, alkyl sulfonate ion and mixing thereof etc..
Preferably, the anion in electrolyte includes alkyl sulfonate ion.Alkyl sulfonate ion is including but not limited to aliphatic sulfonic radical ion, and is not limited on aliphatic group with functional group or substituent group.Preferably conform to below general formula:
R-SO3 -Or Y-R '-SO3 -
In above-mentioned formula, Y refers to substituent group, for instance-F ,-OH etc..In above-mentioned formula, R can be branching or nonbranched fat-based；Can be the fat-based of 1～12 carbon atom, it is preferred to the fat-based of 1～6 carbon atom, it is particularly preferred to methyl, ethyl and n-pro-pyl.
In above-mentioned formula, R ' can be branching or nonbranched fat-based；Can be the fat-based of 2～12 carbon atoms, it is preferred to the fat-based of 2～6 carbon atoms, more preferably non-branching, fat-based containing 2～6 carbon atoms；It is highly preferred that substituent group and sulfonic group are not attached on same carbon atom.
It is particularly preferred that alkyl sulfonate ion is methanesulfonate ions, namely R is methyl.
Electrolyte adopting methanesulfonate ions, suppression self-discharge of battery having obvious effect, thus ensureing battery capacity and cycle life.
The concentration of each ion in electrolyte, it is possible to be changed 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.
Preferably, electrolyte includes lithium ion, zinc ion and sulfate ion, wherein, the concentration of lithium ion is 2mol/L, the concentration of zinc ion is 2mol/L, and the concentration of sulfate ion is 3mol/L, and being zinc sulfate concentration be 2mol/L, lithium sulfate concentration is the electrolyte of 1mol/L.
Preferably, electrolyte includes lithium ion, zinc ion and methanesulfonate ions, wherein, the concentration of lithium ion is 3mol/L, the concentration of zinc ion is 2mol/L, the concentration of methanesulfonate ions is 7mol/L, and being pyrovinic acid zinc concentration be 2mol/L, pyrovinic acid lithium concentration is the electrolyte of 3mol/L.Adopt this electrolyte and graphite agent SFG as positive conductive agent with the use of, relative to the coordinating of other electrolyte, it is possible to better improve floating charge problem and the self discharge problem of battery.
Preferably, electrolyte can also for including lithium ion, zinc ion, sulfate ion and methanesulfonate ions, can be 1mol/L lithium sulfate and 2mol/L zinc sulfate, and the mixed electrolytic solution of 3mol/L pyrovinic acid lithium and 2mol/L zine methqne-sulfonate, the concretely mixing of various ratios, as 1mol/L lithium sulfate and 2mol/L zinc sulfate account for the 25% of electrolyte quality percent, 3mol/L pyrovinic acid lithium and 2mol/L zine methqne-sulfonate account for the 75% of electrolyte quality percent；Or, 1mol/L lithium sulfate and 2mol/L zinc sulfate account for the 50% of electrolyte quality percent, and 3mol/L pyrovinic acid lithium and 2mol/L zine methqne-sulfonate account for the 50% of electrolyte quality percent etc..
Preferably, the pH value range of electrolyte is 3～7.Electrolyte pH is too high, it is possible to can affect the concentration of the second metal ion in electrolyte；Electrolyte pH is too low, then there will be the problem such as proton embedding altogether in electrode material corrosion and charge and discharge process.And the pH value range of electrolyte is 3-7, so both can be effectively ensured the concentration of the second metal ion in electrolyte, thus ensureing capacity and the multiplying power discharging property of battery, it is also possible to avoid the problem that electrode corrosion and proton embed altogether.
Negative pole to battery of the present invention below, is described in detail and illustrates.
The negative pole difference according to its structure and effect, it is possible to for following form three kinds different:
In the first preferred embodiment, negative pole only includes negative current collector, and negative current collector is only used as electronics conduction and the carrier collected, and is not involved 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 includes graphite material, such as the paper tinsel of business-like graphite compacting, and wherein the part by weight shared by graphite ranges for 90～100%.The material of negative current collector is also selected from rustless steel or the rustless steel of passivated process.Rustless steel includes but are not limited to stainless (steel) wire and stainless steel foil, same, and stainless model can be the rustless steel of 300 series, such as stainless steel 304 or Stainless steel 316 or Stainless steel 316 L.It addition, negative current collector is also selected from the metal of the plating/coating high containing hydrogen-evolution overpotential, thus reduce 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: stannum, plumbous or silver-colored on the negative current collector plated surface of Copper Foil or graphite foil.
In the second preferred implementation, negative pole, except negative current collector, also includes load negative electrode active material on negative current collector.Negative electrode active material is the second metal.
Wherein, negative current collector is referred to the first preferred implementation, does not repeat them here.
Second metal is with lamellar or Powdered existence.
When adopting the second sheet metal as negative electrode active material, the second sheet metal forms composite bed with negative current collector.
When adopting the second metal dust as negative electrode active material, the second metal dust is made slurry, then slurry is coated on negative current collector and makes negative pole.
In a particular embodiment, when preparing negative pole, except negative electrode active material the second metal dust, according to practical situation, always according to needing to add cathode conductive agent and negative electrode binder to promote the performance of negative pole.
In the 3rd preferred implementation, directly adopting the second sheet metal as negative pole, the second sheet metal, both as negative current collector, is also negative electrode active material simultaneously.
Preferably, the second metal is manganese, ferrum, copper, zinc, chromium, nickel or stannum.
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 in electrolyte obtains electronics on negative pole and is reduced simultaneously, and is deposited on negative pole.During electric discharge, the second metal being deposited on negative pole is oxidized, loses electronics and is changed in the second metal ion entrance 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.
Certainly, in order to provide better security performance, it is preferable that be additionally provided with barrier film in the electrolytic solution between positive pole and negative pole.The short circuit that barrier film can be avoided the both positive and negative polarity that other unexpected factors cause to be connected and cause.
Barrier film does not have particular/special requirement, as long as permission electrolyte passes 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 is that the other materials such as micropore ceramics dividing plate.
Under a preferred implementation, barrier film is the barrier film that electrolyte is divided into anode electrolyte and electrolyte liquid.Being limited in anode electrolyte by the first metal ion, the second metal ion is limited in electrolyte liquid, and such barrier film can stop the mutual pollution of both positive and negative polarity electrolyte, the optional electrolyte being more suitable for negative or positive electrode, but does not affect ionic charge transmission.For example with anion exchange membrane or hydrion exchange membrane as barrier film, it is arranged in anode electrolyte the first metal ion and can not pass through barrier film, so electrolyte liquid can not be entered, can only be limited in anode electrolyte；It is arranged in electrolyte liquid the second metal ion and can not pass through barrier film, so anode electrolyte can not be entered, can only be limited in electrolyte liquid.But anion or hydrion can pass freely through in electrolyte, therefore have no effect on electrolyte intermediate ion charge transfer.
Below in conjunction with specific embodiment, the present invention will be further elaborated and explanation.
Embodiment 1
By LiMn2O4 LMO, binding agent sodium carboxymethyl cellulose (CMC) and butadiene-styrene rubber (SBR), conductive agent graphite KS-15 doped with tin-antiomony oxide, mix in water according to mass ratio LMO:CMC:SBR:KS-15=84.5:1:2.5:12, form uniform anode sizing agent.Wherein in positive conductive agent graphite KS-15, the tin-antiomony oxide of doping accounts for positive conductive agent mass percent is 0.5%.Being coated in by anode sizing agent on the two sides of the plus plate current-collecting body being coated with conducting film, form active material layer, plus plate current-collecting body is the graphite foil of 100 μ m-thick, is carried out tabletting, is cut into 6 × 6cm size, makes positive pole.
Adopt the composite bed of 20 μ m-thick Copper Foils and 50 μ m-thick zinc paper tinsels as negative pole.Barrier film is AGM fibreglass diaphragm.Barrier film and negative pole size are suitable with positive pole.The one side of barrier film and cathode contact is also coated with one layer of bismuth oxide.Positive pole, negative pole and membrane layer stacked group being dressed up battery core, loads in housing, be then injected separately into electrolyte to filling, electrolyte is the aqueous solution containing 2mol/L zinc sulfate and 1mol/L lithium sulfate.Sealing, is assembled into battery, is designated as S1.
Embodiment 2
With embodiment 1 institute the difference is that, tin-antiomony oxide mass percent in positive conductive agent is 1%, and other positive pole compositions, negative pole, electrolyte, barrier film, with embodiment 1, make battery, is designated as S2.
Comparative example 1
With embodiment 1 institute the difference is that, without tin-antiomony oxide in positive conductive agent, other positive pole compositions, negative pole, electrolyte, barrier film, with embodiment 1, make battery, are designated as D1.
Comparative example 2
With embodiment 1 institute the difference is that, tin-antiomony oxide mass percent in positive conductive agent is 2%, and other positive pole compositions, negative pole, electrolyte, barrier film, with embodiment 1, make battery, is designated as D2.
Comparative example 3
With embodiment 1 institute the difference is that, tin-antiomony oxide mass percent in positive conductive agent is 5%, and other positive pole compositions, negative pole, electrolyte, barrier film, with embodiment 1, make battery, is designated as D3.
Performance test:
Gram volume is tested:
By fully charged for battery in embodiment 1 and comparative example 1 and allow battery discharge with the multiplying power of 0.2C immediately.Test result is in Table 1, and table 1 is in battery gram volume data under 0.2C multiplying power.
Table 1
From table 1 it follows that the battery containing conductive agent adulterant tin-antiomony oxide provided by the invention, gram volume is in a slight decrease.This result shows that the conductive agent in positive electrode provided by the invention has good stability and corrosion resistance.
High rate performance is tested:
By fully charged for battery in embodiment 1 and comparative example 1 and allow battery discharge with the multiplying power of 1C and 3C respectively immediately.Test result is in Table 2, and table 2 is in battery data discharge time under 1C and 3C multiplying power.
Table 2
From table 2 it can be seen that the battery containing conductive agent adulterant tin-antiomony oxide provided by the invention, show of a relatively high 1C high rate performance.
Self discharge is tested:
By fully charged for battery in embodiment 1 and comparative example 1, shelve 7 days or room temperature is shelved 28 days for 60 DEG C, the capacity of test remaining battery.After 60 DEG C of battery is shelved 7 days or room temperature shelves 28 days, discharging fully charged for battery, the recovery data of test battery capacity.Test result is in Table 3, and table 3 is the loss capacity of battery after 60 DEG C are shelved 7 days or room temperature shelves 28 days and capacity restoration data.Wherein capacitance loss rate is the percent value of battery loss capacity and battery initial capacity；Capacity restoration rate is the percentage ratio of battery capacity and battery initial capacity.
Table 3
From table 2 it can be seen that the battery containing doped stannum oxide antimony conductive agent provided by the invention, show relatively low capacitance loss rate and of a relatively high capacity restoration rate.
Additionally, by fully charged for battery in embodiment 2-4, shelve 7 days for 60 DEG C, the capacity of test remaining battery.Test result is as shown in table 4.
Table 4
Described above, after with the addition of ATO in positive conductive agent, the self discharge of battery decreases；The reduction degree of self-discharge of battery changes with the change of ATO content.When in positive conductive agent, the tin-antiomony oxide of doping is when 0.5wt%, the self-discharge rate of battery is minimum.Along with the increase of ATO content in positive conductive agent, self-discharge of battery increases on the contrary, and when in positive conductive agent, the tin-antiomony oxide of doping reaches 2%, self discharge is also bigger than without ATO, produces negative effect.Thus for this kind of battery in embodiment, the mass range of positive conductive agent doping ATO content is 0.5%～1%, it is preferable that the mass ratio of positive conductive agent doping ATO content is 0.5%.
It should be noted that; in the present invention, although tin-antiomony oxide is doped and added in positive pole as positive conductive agent, but tin-antiomony oxide can also serve as a kind of additive and is added directly in the manufacturing process of anode pole piece; it produces same technique effect, thus also within protection scope of the present invention.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.
Claims (9)
1. a positive electrode, described positive electrode includes positive active material and positive conductive agent, it is characterised in that doped with tin-antiomony oxide in described positive conductive agent, and described tin-antiomony oxide accounts for the mass fraction of described positive conductive agent and ranges for 0.5%～1%.
2. positive electrode according to claim 1, it is characterised in that: described positive conductive agent includes the one in graphite KS15, graphite SFG or two kinds.
3. a battery, described battery includes positive pole, negative pole and is arranged on the electrolyte between described positive pole and negative pole, and described positive pole includes plus plate current-collecting body and positive electrode, and described electrolyte includes electrolyte and aqueous solution；Described electrolyte at least can ionize out the first metal ion and the second metal ion；Described first metal ion reversible can be deviate from-embed at described positive pole in charge and discharge process；Described second metal ion is deposited as the second metal at described cathodic reduction in charging process, and described second metal oxidation dissolution in discharge process is the second metal ion；It is characterized in that: described positive electrode is the positive electrode in claim 1-3 described in any one.
4. battery according to claim 3, it is characterised in that: the pH value of described electrolyte is 3～7.
5. battery according to claim 3, it is characterised in that: described solvent is water or the mixture of alcohol or water and alcohol.
6. battery according to claim 3, it is characterised in that: described first metal ion one in lithium ion, sodium ion, magnesium ion and zinc ion.
7. battery according to claim 3, it is characterised in that: described second metal ion is selected from manganese ion, iron ion, copper ion, zinc ion, chromium ion, nickel ion, tin ion or lead ion.
8. battery according to claim 3, it is characterised in that: described electrolyte also includes sulfate ion, chloride ion, acetate ion, nitrate ion, formate ion and one or more in alkyl sulfonate ion.
9. battery according to claim 3, it is characterised in that: described plus plate current-collecting body is graphite foil.
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