CN103794814B - A kind of lithium ion battery and preparation method thereof - Google Patents
A kind of lithium ion battery and preparation method thereof Download PDFInfo
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- CN103794814B CN103794814B CN201210419137.1A CN201210419137A CN103794814B CN 103794814 B CN103794814 B CN 103794814B CN 201210419137 A CN201210419137 A CN 201210419137A CN 103794814 B CN103794814 B CN 103794814B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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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- 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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a kind of lithium ion battery and preparation method thereof.This lithium ion battery comprises housing and the electrode group that is sealed in housing and electrolyte, described electrode group comprises positive pole, negative pole and the anodic aluminium oxide membrane between positive pole and negative pole, described anodic aluminium oxide membrane comprises lithium manganese phosphate and binding agent, relative to the lithium manganese phosphate of 100 weight portions, the content of described binding agent is 1-15 weight portion; The porosity of described anodic aluminium oxide membrane is 30-80%.The battery of preparation not only has the security performance of anodic aluminium oxide membrane, and makes that the charge/discharge capacity of battery is higher, cycle performance is better.
Description
Technical field
The present invention relates to field of batteries, specifically, the invention relates to a kind of lithium ion battery and preparation method thereof.
Background technology
Lithium ion battery is now widely used secondary cell, and it has, and specific energy is high, operating voltage is high, self-discharge rate is low, have extended cycle life, the advantage such as pollution-free.Be widely used in the field such as electric tool, electric automobile, have important requirement to its security performance.
Lithium ion battery generally comprises housing and the electrode group that is sealed in housing and electrolyte, wherein, electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein said barrier film has the effect making to produce electric insulation between two electrodes and keep electrolyte, the barrier film of existing commercial lithium ion battery mainly contains the organic high molecular polymer barrier film such as polyethylene (PE), polypropylene (PP), is generally processed by resin stretched.In the winding process that battery makes, organic barrier film is placed in the middle of both positive and negative polarity and reels, and easily occurs that position is uneven etc. and cause the situations such as both positive and negative polarity contact short circuit in process; Simultaneously organic lower every film strength, thickness is also comparatively large, generally at 20 ~ 40 μm, affects the energy density of battery; And lithium ion battery is long-time under thermal extremes environment preserves or under the condition such as long-time use, abuse, organic barrier film easily shrinks or damages, in fact positive pole and negative pole can contact with each other thus produce internal short-circuit, organic substance barrier film fusing point is generally lower than 170 DEG C, when battery local pyrexia reaches this temperature, barrier film will melt rapidly makes both positive and negative polarity contact, cause battery short circuit, thermal contraction and heat fusing can cause both positive and negative polarity to contact, thus cause short circuit and thermal runaway, even cause the serious consequences such as burning and blast.
Someone proposes the scheme perforated membrane that inorganic filler and resin binder are formed being used as barrier film, wherein, the surface of at least one of perforated membrane and positive pole and negative pole is bonding, perforated membrane can adopt the raw material paste be made up of inorganic filler and dissolving resin binder to be in a solvent coated in polar board surface, then dry.Wherein, inorganic filler is generally aluminium oxide, magnesium oxide, titanium dioxide, zirconia, silica, zinc oxide or tungsten oxide, improves the security performance of battery, but these density of material are comparatively large, and major part is all greater than 4g/cm
3, be unfavorable for the total weight alleviating battery, reduce the quality capacity of battery, and the security performance of battery be also unsatisfactory.
Summary of the invention
The present invention in order to the security performance that overcomes existing battery still undesirable and reduce the technical problem of the quality capacity of battery, provide a kind of security performance better and the charge/discharge capacity of battery is higher, the better lithium ion battery of cycle performance and preparation method thereof.
First object of the present invention is to provide a kind of lithium ion battery, the electrode group comprising housing and be sealed in housing and electrolyte, described electrode group comprises positive pole, negative pole and the anodic aluminium oxide membrane between positive pole and negative pole, described anodic aluminium oxide membrane comprises lithium manganese phosphate and binding agent, relative to the lithium manganese phosphate of 100 weight portions, the content of described binding agent is 1-15 weight portion; The porosity of described anodic aluminium oxide membrane is 30-80%.
Second object of the present invention is to provide the preparation method of above-mentioned battery, step comprises: S1, the preparation of electrode group: by negative pole/anodic aluminium oxide membrane/positive pole through winding or stacked obtained electrode group, described anodic aluminium oxide membrane is attached to positive electrode surface and/or negative terminal surface, described anodic aluminium oxide membrane comprises lithium manganese phosphate and binding agent, relative to the lithium manganese phosphate of 100 weight portions, the content of described binding agent is 1-15 weight portion; The porosity of described anodic aluminium oxide membrane is 30-80%; S2, the preparation of battery: electrode group is inserted in housing, adds electrolyte, then seal.
The present inventor surprisingly finds that the battery prepared by technical scheme of the present invention not only has the security performance of anodic aluminium oxide membrane, the electrical insulation capability of lithium manganese phosphate can be made full use of, the anodic aluminium oxide membrane excellent performance of preparation, the porosity had and absorbency, simultaneously when charging, itself can add electric conducting material and small part can also take off lithium as the lithium manganese phosphate of positive electrode active materials, supplement because negative pole forms the lithium of SEI film and loss, make that the charge/discharge capacity of battery is higher, cycle performance is better.Barrier film of the present invention has excellent electrical insulation capability, heat resistanceheat resistant performance and liquid retainability energy.Manufacture method is simple simultaneously, can directly be coated on negative or positive electrode pole piece, and time prepared by electrode group, winding also facilitates, the uneven short circuit phenomenon caused of diaphragm position can not be there is, winding process can be simplified greatly, improve the make efficiency of battery, energy consumption and cost low.Inorganic material is high temperature resistant, nonflammable, and fail safe is good, and little compared with organic membrane thicknesses, can shorten the transmission path of lithium ion, also can improve the volume energy density of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is ESEM (SEM) figure of the anode pole piece being attached with anodic aluminium oxide membrane made by embodiment 1.
Charging and discharging curve figure when Fig. 2 is made lithium ion battery discharge-rate 1C in embodiment 1.
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.
The invention provides a kind of lithium ion battery, the electrode group comprising housing and be sealed in housing and electrolyte, described electrode group comprises positive pole, negative pole and the anodic aluminium oxide membrane between positive pole and negative pole, described anodic aluminium oxide membrane comprises lithium manganese phosphate and binding agent, relative to the lithium manganese phosphate of 100 weight portions, the content of described binding agent is 1-15 weight portion; The porosity of described anodic aluminium oxide membrane is 30-80%, and security performance is better, has higher battery charging and discharging capacity, better cycle performance.
Preferably, the pick up of anodic aluminium oxide membrane is 20-180%, more preferably 55-180%.Further preferably, the porosity of anodic aluminium oxide membrane is 50-80%, can reduce the weight of battery further, improves the gravimetric energy density of battery.
As long as all belong to protection scope of the present invention containing anodic aluminium oxide membrane between positive pole and negative pole, anodic aluminium oxide membrane of the present invention can be attached to negative terminal surface, also can be attached to positive electrode surface.Namely anodic aluminium oxide membrane of the present invention can be prepared together with negative pole, also can prepare together with positive pole, such as can be dry in the surface-coated inorganic slurry of the surface of positive pole or negative pole.
Further preferably, relative to the lithium manganese phosphate of 100 weight portions, the content of described binding agent is 1-7 weight portion.
Preferably, the mean particle size of lithium manganese phosphate is 30-300nm, more preferably 30-100nm, can the more excellent thinner anodic aluminium oxide membrane of processability, shortens the transmission path of lithium ion further, improves the volume energy density of lithium ion battery.
Preferably, the thickness of anodic aluminium oxide membrane is 1 ~ 30 μm, more preferably 1 ~ 10 μm, can realize the excellent properties of battery with thinner anodic aluminium oxide membrane, reduces the thickness of battery diaphragm, can improve the volume energy density of battery further.
Wherein, binding agent the present invention do not limit, and is preferably selected from one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene or butadiene-styrene rubber.
Invention also provides the preparation method of above-mentioned battery, step comprises: S1, the preparation of electrode group: by negative pole/anodic aluminium oxide membrane/positive pole through winding or stacked obtained electrode group, described anodic aluminium oxide membrane is attached to positive electrode surface and/or negative terminal surface, described anodic aluminium oxide membrane comprises lithium manganese phosphate and binding agent, relative to the lithium manganese phosphate of 100 weight portions, the content of described binding agent is 1-15 weight portion; The porosity of described anodic aluminium oxide membrane is 30-80%.Above-mentioned lithium manganese phosphate and binding agent are by being commercially available.Winding or stacked method the present invention making electrode group do not have without particular/special requirement, can carry out, do not repeat them here with reference to prior art.
Between positive pole and negative pole, the anodic aluminium oxide membrane at interval can by being first attached to negative terminal surface by anodic aluminium oxide membrane, can be preferably, step S1 comprises and first anodic aluminium oxide membrane is attached to negative terminal surface, then by negative terminal surface and the positive pole rear winding staggered relatively that is attached with anodic aluminium oxide membrane or stacked obtained electrode group.Preferably, anodic aluminium oxide membrane is attached to negative terminal surface and comprises the inorganic slurry containing lithium manganese phosphate, binding agent and solvent is coated in negative terminal surface, dry.Also can by first anodic aluminium oxide membrane being attached to positive electrode surface, can preferably, step S1 comprises and first anodic aluminium oxide membrane is attached to positive electrode surface, then by positive electrode surface and the negative pole rear winding staggered relatively that is attached with anodic aluminium oxide membrane or stacked obtained electrode group.Preferably, anodic aluminium oxide membrane is attached to positive electrode surface and comprises the inorganic slurry containing lithium manganese phosphate, binding agent and solvent is coated on positive electrode surface, dry.Wherein, preferably, the solid content of inorganic slurry is 35-85wt%, more preferably 35-70wt%, the anodic aluminium oxide membrane that obtained porosity is higher.Preferably, dry temperature is 60-120 DEG C, more preferably 80-110 DEG C.Drying time is 0.5-24h, more preferably 5-12h.Be generally vacuumize.
Preferably, the thickness being coated on positive electrode surface or being coated on negative terminal surface is 1 ~ 30 μm, more preferably 1 ~ 10 μm.
Wherein, solvent the present invention do not limit, for disperseing lithium manganese phosphate, generally can select volatile solvent, preferably, solvent is selected from one or more in 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF), water or alcohols.
Preferably, the preparation of inorganic slurry comprises and lithium manganese phosphate, binding agent and solvent being mixed under the condition stirred, and the speed of described stirring is 500-1000rpm, and the time of described stirring is 5 ~ 60min, more preferably 10 ~ 20min.Stirring can be electric stirring.Order by merging the present invention of lithium manganese phosphate, binding agent and solvent does not limit, such as, first binding agent can be dissolved in solvent and obtain binder solution, then is joined in binder solution by lithium manganese phosphate and mix.Also optionally can contain other usual auxiliaries, such as dispersant etc. in inorganic slurry, with the hybrid mode of the lithium manganese phosphate in inorganic slurry, binding agent and solvent etc., the present invention can adopt existing hybrid mode, is not repeating at this.
S2, the preparation of battery: insert in housing by electrode group, add electrolyte, then seal, preparation method, without particular/special requirement, can carry out with reference to prior art, and the method for sealing is that those skilled in the art are known.The consumption of electrolyte is conventional amount used.Lithium ion battery provided by the invention can be obtained.Follow-uply also have ageing, the conventional steps such as to change into, do not repeat them here.
Improvements of the present invention are barrier film, therefore have no particular limits other the Nomenclature Composition and Structure of Complexes of lithium rechargeable battery.Such as the positive pole of battery, negative pole and electrolyte are had no particular limits, all types of positive poles, negative pole and the electrolyte that can use in lithium rechargeable battery can be used.Those of ordinary skill in the art can according to the instruction of prior art, can select and prepare the positive pole of lithium rechargeable battery of the present invention, negative pole and electrolyte easily, and obtain lithium rechargeable battery of the present invention by positive pole, negative pole, above-mentioned anodic aluminium oxide membrane and electrolyte and said structure of the present invention, do not repeat them here.
Wherein, positive pole consist of conventionally known to one of skill in the art.In general, the preparation of positive pole adopts and well known to a person skilled in the art technology, and such as positive pole comprises and is coated on positive electrode collector by anode sizing agent, and drying, calendering prepare.Anode sizing agent generally comprises positive active material, conductive agent, positive electrode binder and positive pole solvent.
The kind of described positive electrode collector has been conventionally known to one of skill in the art, such as, can be selected from aluminium foil, Copper Foil, Punching steel strip.In the specific embodiment of the present invention, use aluminium foil as positive electrode collector.
The kind of the binding agent in described positive electrode and content are conventionally known to one of skill in the art, and such as fluorine resin and polyolefin compound are as one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).In general, according to the difference of adhesive therefor kind, with the weight of positive active material for benchmark, the content of binding agent is 0.1-15wt%, is preferably 1-7wt%.The present invention is not particularly limited described positive active material, for any positive active material that can be purchased in prior art, such as, can adopt all positive active materials that can be purchased, as LiFePO
4, Li
3v
2(PO
4)
3, LiMn
2o
4, LiMnO
2, LiNiO
2, LiCoO
2, LiVPO
4f, LiFeO
2deng, or ternary system Li
1+xl
1-y-zm
yn
zo2, wherein-0.1≤x≤0.2,0≤y≤1,0≤z≤1,0≤y+z≤1.0, L, M, N are at least one in Co, Mn, Ni, Al, Mg, Ga and 3d transiting group metal elements.
The present invention is not particularly limited described positive conductive agent, can be the positive conductive agent of this area routine, at least one in such as acetylene black, conductive carbon black and electrically conductive graphite.Wherein, with the weight of positive active material for benchmark, the content of described positive conductive agent is 0.1-20wt%, is preferably 2-10wt%.
The preparation method of concrete positive pole can for be prepared into positive electrode slurries with positive pole solvent by positive active material, positive electrode binder and conductive agent, the requirement of the viscosity that the addition of positive pole solvent can be coated with according to the slurry of positive pole slurries to be prepared and operability adjusts flexibly, then the positive pole slurries obtained are coated on plus plate current-collecting body, dry compressing tablet, then cut-parts obtain positive pole.When the positive active material of above-mentioned positive electrode composition, positive electrode binder and conductive agent being prepared into positive electrode slurries with solvent, reinforced order is not asked especially.Dry temperature can be 80-150 DEG C, and drying time can be 2-10 hour.Method and the condition of calendering are method known in those skilled in the art.Positive pole solvent can be various positive pole solvent of the prior art, as being selected from one or more in 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and alcohols.The consumption of positive pole solvent enables anode sizing agent be coated on conducting base.In general, the consumption of positive pole solvent makes the content of positive active material in anode sizing agent be 40-90wt%, is preferably 50-85wt%.
Wherein, negative pole consist of conventionally known to one of skill in the art.In general, negative pole comprises conducting base and is coated on the negative material on conducting base, and described negative material comprises negative electrode active material and negative electrode binder, and preparation method is known to the skilled person,
Described negative electrode active material is not particularly limited, what can use this area routine embeds the negative electrode active material disengaging lithium, the for example electric conductive polymer, lamellar compound (material with carbon element, metal oxide etc.) etc. of lithium metal, lithium alloy, lithium doping, described material with carbon element is be selected from one or more in non-graphitic carbon, graphite or the charcoal obtained by high-temperature oxydation by polyyne family macromolecule material or pyrolytic carbon, coke, organic polymer sinter, active carbon.Described organic polymer sinter can be by phenolic resins, epoxy resin etc. being sintered and carbonizing rear products therefrom.Wherein, by metallic lithium foil as negative active core-shell material and negative conductive matrix, namely metallic lithium foil can directly can be used as negative pole battery simple for production.
The kind of described negative electrode binder and content are conventionally known to one of skill in the art, and such as fluorine resin and polyolefin compound are as one or more in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinylidene fluoride/hexafluoropropylene copolymer, butadiene-styrene rubber (SBR), hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol; In general, according to the difference of adhesive therefor kind, with the weight of negative electrode active material for benchmark, the content of negative electrode binder is 0.01-10 % by weight, is preferably 0.02-5 % by weight.
Described negative material can also comprise conductive agent to increase the conductivity of electrode, reduces the internal resistance of cell.Described conductive agent is not particularly limited, and can be the cathode conductive agent of this area routine, one or more in such as carbon black, nickel powder, copper powder.With the weight of negative electrode active material for benchmark, the content of described conductive agent is 0-12 % by weight, is preferably 2-10 % by weight.
Negative conductive matrix can be negative conductive matrix conventional in lithium ion battery, and as stamped metal, metal forming, net metal, foamed metal, uses Copper Foil as negative conductive matrix in specific embodiment of the invention scheme.
The preparation method of described negative pole can adopt conventional preparation method, such as, negative electrode active material and binding agent are dissolved in solvent according to a certain percentage and are mixed into slurries, then apply this slurries on wide cut conducting base, and then dry, roll-in is also cut, and obtains pole piece.Condition that is dry and roll-in is known in those skilled in the art, and such as the temperature of dry negative plate is generally 60-120 DEG C, preferred 80-110 DEG C, and drying time is 0.5-5 hour.Wherein, described solvent can be selected from one or more in 1-METHYLPYRROLIDONE (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and alcohols.The consumption of solvent can make described pastel have viscosity and mobility, can be coated on described conducting base.In general, with the weight of negative electrode active material for benchmark, the content 50-150 % by weight of described solvent, is preferably 70-120 % by weight.The content of described negative electrode active material and adhesive is the 40-70 % by weight of cathode size total weight, is preferably 45-60 % by weight.The consumption of solvent can make described pastel have viscosity and mobility, can be coated on described conducting base.
Described electrolyte is the mixed solution of electrolyte lithium salt and nonaqueous solvents, is not particularly limited it, can use the nonaqueous electrolytic solution of this area routine.Such as electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), hexafluoroarsenate lithium (LiAsF
6), hexafluorosilicic acid lithium (LiSiF
6), tetraphenylboronic acid lithium (LiB (C
6h
5)
4), lithium chloride (LiCl), lithium bromide (LiBr), chlorine lithium aluminate (LiAlCl
4) and fluorocarbon based Sulfonic Lithium (LiC (SO
2cF
3)
3), LiCH
3sO
3, LiN (SO
2cF
3)
2in one or more.Organic solvent selects chain acid esters and ring-type acid esters mixed solution, and wherein chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl propyl carbonate (MPC), dipropyl carbonate (DPC) and other is fluorine-containing, sulfur-bearing or containing one or more in the chain organosilane ester of unsaturated bond.Ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other is fluorine-containing, sulfur-bearing or containing one or more in the ring-type organosilane ester of unsaturated bond.In nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is generally 0.1-2 mol/L, is preferably 0.8-1.2 mol/L.The injection rate of electrolyte is generally 1.5-4.9 gram/ampere-hour.
In more detail the present invention will be described by embodiment below.
The various raw materials used in embodiment are the various raw materials that this area routine uses, all can by commercially available.
Below by embodiment, the present invention is further illustrated.
Embodiment 1
(1) preparation of positive plate
Take LiFePO4 (LiFePO
4), acetylene black, polyvinylidene fluoride (PVDF), 1-METHYLPYRROLIDONE (NMP) be according to weight ratio LiFePO
4: acetylene black: PVDF:NMP=85:10:5:50 prepares anode sizing agent, after stirring, coating machine is coated on 12 μm of thick aluminium foils, and then 120 DEG C of dry 5h, then use tabletting machine, finally cut into slices, obtain the lithium ion cell positive of length × wide × thick=551mm × 44mm × 130 μm.
(2) preparation of anodic aluminium oxide membrane
Stirred by 0.5g polyvinylidene fluoride and be dissolved in 5gN-methyl pyrrolidone, add the lithium manganese phosphate powder that 8.6g particle diameter is 50nm, stir 20min with electric mixer (speed is 1000rpm), obtain inorganic slurry, solid content controls at 61wt%.With coater on above-mentioned anode pole piece surface, coating thickness 10 μm, obtains the anode pole piece being coated with anodic aluminium oxide membrane after 120 DEG C of dry 5h in vacuum.
The porosity that the full-automatic mercury injection apparatus of AutoporeIV9500 adopting Merck & Co., Inc of the U.S. to produce records anodic aluminium oxide membrane is 50%.
The pick up recording anodic aluminium oxide membrane is 55%.
Adopt the above-mentioned obtained anodic aluminium oxide membrane of JSM-7600F type field emission microscopy observation, SEM photo, as Fig. 1, can be observed the passage that anodic aluminium oxide membrane surface has much electrolysis liquid to pass through, is beneficial to lithium ion and passes through.
(3) preparation of battery
The anode pole piece that be attached with anodic aluminium oxide membrane obtained by abovementioned steps (2) and metal lithium sheet, wherein, the face and the metal lithium sheet that are attached with anodic aluminium oxide membrane are staggered relatively, make button cell, then inject 0.05g electrolyte, finally sealed battery case, makes lithium ion battery sample S1.Electrolyte is 1mol/LLiPF
6ethylene carbonate (EC) and the mixed solution (volume ratio is=1: 1) of dimethyl carbonate (DMC).The assembling process of battery is all carried out in the glove box being full of argon gas.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare battery sample S2, the coating thickness unlike inorganic slurry is 5 μm.
The porosity adopting the method identical with embodiment 1 to record anodic aluminium oxide membrane is 52%, and pick up is 56%.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare battery sample S3, the coating thickness unlike inorganic slurry is 20 μm.
The porosity adopting the method identical with embodiment 1 to record anodic aluminium oxide membrane is 52%, and pick up is 55%.
Embodiment 4
Adopt the method identical with embodiment 1 to prepare battery sample S4, the coating thickness unlike inorganic slurry is 30 μm.
The porosity adopting the method identical with embodiment 1 to record anodic aluminium oxide membrane is 51%, and pick up is 56%.
Embodiment 5
Adopt the method identical with embodiment 1 to prepare battery sample S5, the particle diameter unlike lithium manganese phosphate is 100nm.
The porosity adopting the method identical with embodiment 1 to record anodic aluminium oxide membrane is 55%, and pick up is 60%.
Embodiment 6
Adopt the method identical with embodiment 1 to prepare battery sample S6, the particle diameter unlike lithium manganese phosphate is 200nm.
The porosity adopting the method identical with embodiment 1 to record anodic aluminium oxide membrane is 57%, and pick up is 62%.
Embodiment 7
Adopt the method identical with embodiment 1 to prepare battery sample S7, the amount unlike lithium manganese phosphate is 3.5g, and the solid content of obtained inorganic slurry is 39wt%.
The porosity adopting the method identical with embodiment 1 to record anodic aluminium oxide membrane is 75%, and pick up is 137%.
Embodiment 8
Adopt the method identical with embodiment 1 to prepare battery sample S8, the amount unlike lithium manganese phosphate is 31g, and the solid content of obtained inorganic slurry is 85wt%.
The porosity adopting the method identical with embodiment 1 to record anodic aluminium oxide membrane is 32%, and pick up is 20%.
Embodiment 9
(1) preparation of positive plate
Take LiFePO4 (LiFePO
4), acetylene black, polyvinylidene fluoride (PVDF), 1-METHYLPYRROLIDONE (NMP) be according to weight ratio LiFePO
4: acetylene black: PVDF:NMP=85:10:5:65 prepares anode sizing agent, after stirring, coating machine is coated on 12 μm of thick aluminium foils, and then 120 DEG C of dry 5h, then use tabletting machine, finally cut into slices, obtain the lithium ion cell positive of length × wide × thick=551mm × 44mm × 130 μm.
(2) preparation of anodic aluminium oxide membrane
Stirred by 0.5g polyvinylidene fluoride and be dissolved in 5gN-methyl pyrrolidone, add the lithium manganese phosphate powder that 9.5g particle diameter is 40nm, stir 20min with electric mixer (speed is 900rpm), obtain inorganic slurry, solid content controls at 63wt%.With coater on metal lithium sheet surface, coating thickness 10 μm, obtains the cathode pole piece being coated with anodic aluminium oxide membrane after 120 DEG C of dry 5h in vacuum.
The porosity adopting the method identical with embodiment 1 to record anodic aluminium oxide membrane is 52%, and pick up is 57%.
(3) preparation of battery
The positive pole that the cathode pole piece that be attached with anodic aluminium oxide membrane obtained by abovementioned steps (2) and step (1) obtain, wherein, the face and the positive pole that are attached with anodic aluminium oxide membrane are staggered relatively, make button cell, then inject 0.05g electrolyte, finally sealed battery case, makes lithium ion battery sample S9.Electrolyte is 1mol/LLiPF
6ethylene carbonate (EC) and the mixed solution (volume ratio is=1: 1) of dimethyl carbonate (DMC).The assembling process of battery is all carried out in the glove box being full of argon gas.
Comparative example 1
(1) preparation of positive plate
Take LiFePO4 (LiFePO
4), acetylene black, polyvinylidene fluoride (PVDF), 1-METHYLPYRROLIDONE (NMP) be according to weight ratio LiFePO
4: acetylene black: PVDF:NMP=85:10:5:50 prepares anode sizing agent, after stirring, coating machine is coated on 12 μm of thick aluminium foils, and then 120 DEG C of dry 5h, then use tabletting machine, finally cut into slices, obtain the lithium ion cell positive of length × wide × thick=551mm × 44mm × 130 μm.
(2) preparation of anodic aluminium oxide membrane
Stirred by 0.5g polyvinylidene fluoride and be dissolved in 5gN-methyl pyrrolidone, add 8.6g alumina powder, stir 20min with electric mixer (speed is 1000rpm), obtain inorganic slurry, solid content controls at 61wt%.With coater on above-mentioned anode pole piece surface, coating thickness 10 μm, obtains the anode pole piece being coated with anodic aluminium oxide membrane after 120 DEG C of dry 5h in vacuum.
The porosity adopting the method identical with embodiment 1 to record anodic aluminium oxide membrane is 65%, and pick up is 76%.
(3) preparation of battery
The anode pole piece that be attached with anodic aluminium oxide membrane obtained by abovementioned steps (2) and metal lithium sheet, wherein, the face and the metal lithium sheet that are attached with anodic aluminium oxide membrane are staggered relatively, make button cell, then inject 0.05g electrolyte, finally sealed battery case, makes lithium ion battery sample DS1.Electrolyte is 1mol/LLiPF
6ethylene carbonate (EC) and the mixed solution (volume ratio is=1: 1) of dimethyl carbonate (DMC).The assembling process of battery is all carried out in the glove box being full of argon gas.
Performance test
1, anodic aluminium oxide membrane porosity: the full-automatic mercury injection apparatus of AutoporeIV9500 using Merck & Co., Inc of the U.S. to produce tests the open-cell porosity of the anodic aluminium oxide membrane of above-described embodiment 1-9 and comparative example 1 preparation, and maximum pressure is 30000PSI, and test result is in table 1.
2, negative or positive electrode prepared by above-described embodiment 1-9 and comparative example 1 is soaked 30min in the electrolytic solution, weigh the added value of pole piece weight after taking out, be labeled as m
1; The positive pole being attached with anodic aluminium oxide membrane prepare above-described embodiment 1-9 and comparative example 1 or negative pole soak 30min in the electrolytic solution, weigh the added value of pole piece weight, be labeled as m after taking out
2; m
2deduct m
1the weight m obtained
3be the liquid absorption of anodic aluminium oxide membrane, m
3with m
1ratio be the pick up of anodic aluminium oxide membrane.Pick up test result is in table 1.
3, charging and discharging capacity
Battery S1-S9 and DS1 that just prepared by embodiment 1-9 and comparative example 1 is placed in respectively on computer program-control charge-discharge test instrument and carries out electrochemical property test, and voltage range is 3 ~ 4.2V, and charge-discharge magnification is 1C.
Battery is set to charged state and work electrode takes off lithium, the density of charging current is 0.5mA/cm
2, charge to cut-ff voltage and out of service, calculate initial charge specific capacity.
The quality of the de-lithium capacity/active material of de-lithium specific capacity (mAh/g) first=first
After de-lithium terminates first, then battery is set to discharge condition and the embedding lithium of work electrode, discharge current density is 0.5mA/cm
2, discharge when being discharged to cut-ff voltage and terminate, calculate first discharge specific capacity.
The quality of the embedding lithium capacity/active material of embedding lithium specific capacity (mAh/g) first=first
Test result is as table 2.
Charging and discharging curve when Fig. 2 is made lithium ion battery discharge-rate 1C in embodiment 1.
4, cycle performance: battery S1-S9 and DS1 prepared by embodiment 1-9 and comparative example 1 is carried out loop test respectively, with the constant current of 0.5mA, constant current charge is carried out to battery, charge to cut-ff voltage, same with the constant current of 0.5mA to battery constant-current discharge, be discharged to cut-ff voltage, shelve 10 minutes, repeat above step, make continuous print charge-discharge test, obtain the battery capacity after battery 100 circulations, calculate the discharge capacitance of the rear battery of 100 circulations.
Discharge capacity/discharge capacity × 100% first after time circulation of discharge capacitance=100, test result is as table 2.
Security performance: can battery, normally discharge and recharge after 200 DEG C of high-temperature bakings.
Table 1
| Anodic aluminium oxide membrane porosity (%) | Pick up (%) | |
| Embodiment 1 | 50 | 55 |
| Embodiment 2 | 52 | 56 |
| Embodiment 3 | 52 | 55 |
| Embodiment 4 | 51 | 56 |
| Embodiment 5 | 55 | 60 |
| Embodiment 6 | 57 | 62 |
| Embodiment 7 | 75 | 137 |
| Embodiment 8 | 32 | 20 |
| Embodiment 9 | 52 | 57 |
| Comparative example 1 | 65 | 76 |
Table 2
| Initial charge specific capacity (mAh/g) | First discharge specific capacity (mAh/g) | Discharge capacity (mAh/g) after 100 circulations | 100 cyclic discharge capacity conservation rates (%) | Can normally discharge and recharge after 200 DEG C of bakings | |
| S1 | 146.9 | 140.7 | 144.4 | 99.8 | Be |
| S2 | 147.1 | 141.2 | 140.8 | 99.7 | Be |
| S3 | 146.8 | 140.5 | 140.2 | 99.8 | Be |
| S4 | 147.3 | 141.1 | 140.5 | 99.6 | Be |
| S5 | 148.2 | 142.1 | 141.7 | 99.7 | Be |
| S6 | 147.6 | 141.8 | 141.7 | 99.9 | Be |
| S7 | 148.1 | 142.2 | 141.7 | 99.7 | Be |
| S8 | 147.9 | 141.7 | 140.9 | 99.5 | Be |
| S9 | 146.6 | 141.2 | 140.9 | 99.8 | Be |
| DS1 | 142.3 | 132.3 | 131.3 | 99.2 | Be |
Barrier film of the present invention has excellent electrical insulation capability, heat resistanceheat resistant performance and liquid retainability energy.Manufacture method is simple simultaneously, can directly be coated on negative or positive electrode pole piece, and time prepared by electrode group, winding also facilitates, the uneven short circuit phenomenon caused of diaphragm position can not be there is, winding process can be simplified greatly, improve the make efficiency of battery, energy consumption and cost low.Battery charging and discharging specific capacity prepared by the present invention is high, the good cycle of battery, and inorganic material is high temperature resistant, nonflammable, and fail safe is good, simultaneously little compared with organic membrane thicknesses, can shorten the transmission path of lithium ion, also can improve the volume energy density of lithium ion battery.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (20)
1. a lithium ion battery, it is characterized in that, the electrode group comprising housing and be sealed in housing and electrolyte, described electrode group comprises positive pole, negative pole and the anodic aluminium oxide membrane between positive pole and negative pole, described anodic aluminium oxide membrane comprises lithium manganese phosphate and binding agent, relative to the lithium manganese phosphate of 100 weight portions, the content of described binding agent is 1-15 weight portion; The porosity of described anodic aluminium oxide membrane is 30-80%.
2. battery according to claim 1, is characterized in that, the pick up of described anodic aluminium oxide membrane is 20-180%.
3. battery according to claim 1, is characterized in that, the porosity of described anodic aluminium oxide membrane is 50-80%.
4. battery according to claim 1, is characterized in that, described anodic aluminium oxide membrane is attached to negative terminal surface.
5. battery according to claim 1, is characterized in that, described anodic aluminium oxide membrane is attached to positive electrode surface.
6. battery according to claim 1, is characterized in that, relative to the lithium manganese phosphate of 100 weight portions, the content of described binding agent is 1-7 weight portion.
7. battery according to claim 1, is characterized in that, the mean particle size of described lithium manganese phosphate is 30-300nm.
8. battery according to claim 1, is characterized in that, the mean particle size of described lithium manganese phosphate is 30-100nm.
9. battery according to claim 1, is characterized in that, the thickness of described anodic aluminium oxide membrane is 1 ~ 30 μm.
10. battery according to claim 1, is characterized in that, the thickness of described anodic aluminium oxide membrane is 1 ~ 10 μm.
The preparation method of 11. 1 kinds of batteries as claimed in claim 1, is characterized in that, step comprises:
S1, the preparation of electrode group: by negative pole/anodic aluminium oxide membrane/positive pole through winding or stacked obtained electrode group, described anodic aluminium oxide membrane is attached to positive electrode surface and/or negative terminal surface, described anodic aluminium oxide membrane comprises lithium manganese phosphate and binding agent, relative to the lithium manganese phosphate of 100 weight portions, the content of described binding agent is 1-15 weight portion; The porosity of described anodic aluminium oxide membrane is 30-80%;
S2, the preparation of battery: electrode group is inserted in housing, adds electrolyte, then seal.
12. preparation methods according to claim 11, is characterized in that, step S1 comprises and first anodic aluminium oxide membrane is attached to negative terminal surface, then by negative terminal surface and the positive pole rear winding staggered relatively that is attached with anodic aluminium oxide membrane or stacked obtained electrode group.
13. preparation methods according to claim 12, is characterized in that, anodic aluminium oxide membrane are attached to negative terminal surface and comprise and be coated in negative terminal surface by the inorganic slurry containing lithium manganese phosphate, binding agent and solvent, dry;
The solid content of described inorganic slurry is 35-85wt%.
14. preparation methods according to claim 13, is characterized in that, described in be coated on negative terminal surface thickness be 1-30 μm.
15. preparation methods according to claim 11, is characterized in that, step S1 comprises and first anodic aluminium oxide membrane is attached to positive electrode surface, then by positive electrode surface and the negative pole rear winding staggered relatively that is attached with anodic aluminium oxide membrane or stacked obtained electrode group.
16. preparation methods according to claim 15, is characterized in that, anodic aluminium oxide membrane are attached to positive electrode surface and comprise and be coated on positive electrode surface by the inorganic slurry containing lithium manganese phosphate, binding agent and solvent, dry;
The solid content of described inorganic slurry is 35-85wt%.
17. preparation methods according to claim 16, is characterized in that, described in be coated on positive electrode surface thickness be 1-30 μm.
18. preparation methods according to claim 13 or 16, it is characterized in that, described solvent is selected from one or more in 1-METHYLPYRROLIDONE, dimethyl formamide, diethylformamide, dimethyl sulfoxide (DMSO), oxolane, water or alcohols.
19. preparation methods according to claim 13 or 16, it is characterized in that, the preparation of described inorganic slurry comprises and lithium manganese phosphate, binding agent and solvent being mixed under the condition stirred, and the speed of described stirring is 500-1000rpm, and the time of described stirring is 5 ~ 60min.
20. preparation methods according to claim 13 or 16, it is characterized in that, the temperature of described drying is 60-120 DEG C, and drying time is 0.5-24h.
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| CN107706338B (en) * | 2017-11-24 | 2018-10-19 | 深圳锂硫科技有限公司 | A kind of lithium ion battery separator and preparation method thereof containing positive electrode |
| CN109841780A (en) * | 2017-11-24 | 2019-06-04 | 比亚迪股份有限公司 | A kind of lithium ion battery separator and its manufacturing method and the lithium ion battery containing this partition |
| CN110459723A (en) * | 2019-08-07 | 2019-11-15 | 珠海格力电器股份有限公司 | Battery diaphragm and preparation method thereof and battery with the battery diaphragm |
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