CN103794814A - Lithium ion battery and its preparation method - Google Patents
Lithium ion battery and its preparation method Download PDFInfo
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- CN103794814A CN103794814A CN201210419137.1A CN201210419137A CN103794814A CN 103794814 A CN103794814 A CN 103794814A CN 201210419137 A CN201210419137 A CN 201210419137A CN 103794814 A CN103794814 A CN 103794814A
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- aluminium oxide
- oxide membrane
- anodic aluminium
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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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- 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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Abstract
The invention provides a lithium ion battery and its preparation method. The lithium ion battery comprises a housing, an electrode group and an electrolyte, and the electrode group and the electrolyte are sealed in the housing, the electrode group comprises a positive electrode, a negative electrode and an inorganic membrane arranged between the positive electrode and the negative electrode, the inorganic membrane includes lithium manganese phosphate and a binder, in relative to 100 parts by weight of the lithium manganese phosphate, the content of the binder is 1-15 parts by weight; and the inorganic membrane porosity is 30-80%. The prepared lithium ion battery has the advantage of inorganic membrane safety performance, the charge and discharge capacity of the battery is higher, and the cycling 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, its security performance is had to important requirement.
Lithium ion battery generally comprises housing and is sealed in electrode group and the electrolyte in housing, 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 that makes to produce between two electrodes electric insulation and maintenance 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 of making at battery, organic barrier film is reeled in the middle of being placed on both positive and negative polarity, easily occurs that the uneven grade in position causes the situations such as both positive and negative polarity contact short circuit in process; Simultaneously organic lower every film strength, thickness is also larger, generally at 20 ~ 40 μ m, affects the energy density of battery; And lithium ion battery under thermal extremes environment long-time preserve or the condition such as long-time use, abuse under, organic barrier film easily shrinks or damages, thereby in fact anodal and negative pole can contact with each other and produce internal short-circuit, organic substance barrier film fusing point is generally lower than 170 ℃, in the time that battery local pyrexia reaches this temperature, barrier film will melt rapidly makes both positive and negative polarity contact, cause battery short circuit, thermal contraction can cause both positive and negative polarity to contact with heat fusing, thereby cause short circuit and thermal runaway, even cause the serious consequences such as burning and blast.
Someone has proposed the scheme as barrier film by the perforated membrane of inorganic filler and resin binder formation, wherein, the surface of at least one of perforated membrane and anodal and negative pole is bonding, perforated membrane can adopt by inorganic filler and be dissolved in the raw material paste that the resin binder in solvent forms and be 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 larger, and major part is all greater than 4g/cm
3, be unfavorable for alleviating the total weight of battery, reduced the quality capacity of battery, and the security performance of battery is also unsatisfactory.
Summary of the invention
The present invention is still undesirable and reduced the technical problem of the quality capacity of battery for the security performance that overcomes existing battery, provides that a kind of security performance charge/discharge capacity better and 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, comprise housing and be sealed in electrode group and the electrolyte in housing, 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, with respect 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 reel or the stacked electrode group that makes, described anodic aluminium oxide membrane is attached to anodal surface and/or negative terminal surface, described anodic aluminium oxide membrane comprises lithium manganese phosphate and binding agent, with respect 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, added electrolyte, then sealing.
The present inventor surprisingly finds that the battery of preparing by technical scheme of the present invention not only has the security performance of anodic aluminium oxide membrane, can make full use of the electrical insulation capability of lithium manganese phosphate, the anodic aluminium oxide membrane excellent performance of preparation, the porosity having had and absorbency, simultaneously in the time of charging, itself can add electric conducting material and can also small part take off lithium as the lithium manganese phosphate of positive electrode active materials, supplement because negative pole forms SEI film and the lithium of loss, make the charge/discharge capacity of battery 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, reels also convenient time prepared by electrode group, can there is not the uneven short circuit phenomenon causing of diaphragm position, can simplify greatly winding process, improve the make efficiency of battery, energy consumption and cost are 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 the ESEM that in embodiment 1, made is attached with the anode pole piece of anodic aluminium oxide membrane (SEM) figure.
Fig. 2 is charging and discharging curve figure when 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 clearer, 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, is not intended to limit the present invention.
The invention provides a kind of lithium ion battery, comprise housing and be sealed in electrode group and the electrolyte in housing, 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, with respect 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%, further can reduce the weight of battery, improves the weight energy density of battery.
All belong to protection scope of the present invention as long as contain 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 anodal surface.Be that anodic aluminium oxide membrane of the present invention can be prepared together with negative pole, also can prepare together with positive pole, for example can be dry in the surface-coated inorganic slurry of anodal surface or negative pole.
Further preferably, with respect to the lithium manganese phosphate of 100 weight portions, the content of described binding agent is 1-7 weight portion.
Preferably, the particle average grain diameter of lithium manganese phosphate is 30-300nm, and more preferably 30-100nm can the more excellent thinner anodic aluminium oxide membrane of processability, further shortens the transmission path of lithium ion, improves the volume energy density of lithium ion battery.
Preferably, the thickness of anodic aluminium oxide membrane is 1 ~ 30 μ m, and more preferably 1 ~ 10 μ m can realize with thinner anodic aluminium oxide membrane the excellent properties of battery, reduces the thickness of battery diaphragm, further can improve the volume energy density of battery.
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.
The present invention provides the preparation method of above-mentioned battery simultaneously, step comprises: S1, the preparation of electrode group: by negative pole/anodic aluminium oxide membrane/positive pole through reel or the stacked electrode group that makes, described anodic aluminium oxide membrane is attached to anodal surface and/or negative terminal surface, described anodic aluminium oxide membrane comprises lithium manganese phosphate and binding agent, with respect 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 can be commercially available.Coiling or stacked method the present invention who makes electrode group, not without specific (special) requirements, can carry out with reference to prior art, do not repeat them here.
Between positive pole and negative pole, the anodic aluminium oxide membrane at interval can be by being first attached to negative terminal surface by anodic aluminium oxide membrane, can be preferably, step S1 comprises first anodic aluminium oxide membrane is attached to negative terminal surface, then will be attached with the negative terminal surface and anodal rear coiling staggered relatively or the stacked electrode group that makes of anodic aluminium oxide membrane.Preferably, anodic aluminium oxide membrane is attached to negative terminal surface and comprises the inorganic slurry that contains lithium manganese phosphate, binding agent and solvent is coated in negative terminal surface, dry.Also can be by first anodic aluminium oxide membrane being attached to anodal surface, can be preferably, step S1 comprises and first anodic aluminium oxide membrane is attached to anodal surface, then will be attached with the positive pole surface and negative pole rear coiling staggered relatively or the stacked electrode group that makes of anodic aluminium oxide membrane.Preferably, anodic aluminium oxide membrane is attached to anodal surface and comprises that the inorganic slurry that contains lithium manganese phosphate, binding agent and solvent is coated on to anodal surface to be gone up, dry.Wherein, preferably, the solid content of inorganic slurry is 35-85wt%, and more preferably 35-70wt% makes the anodic aluminium oxide membrane that porosity is higher.Preferably, dry temperature is 60-120 ℃, more preferably 80-110 ℃.Be 0.5-24h, more preferably 5-12h drying time.Be generally vacuumize.
Preferably, the thickness that is coated on anodal surface or is coated on negative terminal surface is 1 ~ 30 μ m, more preferably 1 ~ 10 μ m.
Wherein, solvent the present invention do not limit, be used 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 comprise by lithium manganese phosphate, binding agent and solvent stir condition under mix, the speed of described stirring is 500-1000rpm, 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, for example, can first binding agent be dissolved in to solvent and make binder solution, then lithium manganese phosphate is joined in binder solution and mixed.In inorganic slurry, also can optionally contain other usual auxiliaries, such as dispersant etc., with the hybrid mode of lithium manganese phosphate, binding agent and solvent etc. in inorganic slurry, the present invention can adopt existing hybrid mode, is not repeating at this.
S2, the preparation of battery: electrode group is inserted in housing, added electrolyte, then sealing, preparation method, without specific (special) requirements, 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.Can obtain lithium ion battery provided by the invention.Follow-uply also have ageing, the conventional steps such as change into, do not repeat them here.
Improvements of the present invention are barrier film, therefore other the Nomenclature Composition and Structure of Complexes of lithium rechargeable battery are had no particular limits.For example the positive pole to battery, negative pole and electrolyte have no particular limits, and can use all types of positive poles, negative pole and the electrolyte that can in lithium rechargeable battery, use.Those of ordinary skill in the art can be according to the instruction of prior art, can select easily and prepare positive pole, negative pole and the electrolyte of lithium rechargeable battery of the present invention, and make 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, anodal consist of conventionally known to one of skill in the art.In general, anodal preparation adopts and well known to a person skilled in the art that technology, for example positive pole comprise anode sizing agent is coated on positive electrode collector, and drying, calendering prepare.Anode sizing agent generally comprises positive active material, conductive agent, anodal binding agent and anodal solvent.
The kind of described positive electrode collector has been conventionally known to one of skill in the art, for example, 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 for example 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, take the weight of positive active material as 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, can, for any positive active material that can be purchased in prior art, for example, 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 anodal conductive agent, can be the anodal conductive agent of this area routine, such as at least one in acetylene black, conductive carbon black and electrically conductive graphite.Wherein, take the weight of positive active material as benchmark, the content of described anodal conductive agent is 0.1-20wt%, is preferably 2-10wt%.
Concrete anodal preparation method can be for to be prepared into positive electrode slurries with anodal solvent by positive active material, anodal binding agent and conductive agent, the addition of anodal solvent can be adjusted flexibly according to the viscosity of the slurry coating of anodal slurries to be prepared and the requirement of operability, then the anodal slurries that obtain are coated on plus plate current-collecting body, dry compressing tablet, then cut-parts obtain positive pole.In the time the positive active material of above-mentioned positive electrode composition, anodal binding agent and conductive agent being prepared into positive electrode slurries with solvent, reinforced order is not asked especially.Dry temperature can be 80-150 ℃, and can be 2-10 hour drying time.Method and the condition of calendering are method known in those skilled in the art.Anodal solvent can be various anodal 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 anodal solvent can be coated on conducting base anode sizing agent.In general, it is 40-90wt% that the consumption of anodal solvent makes the content of positive active material in anode sizing agent, 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 pole adhesive, and preparation method is known to the skilled person,
Described negative electrode active material is not particularly limited, can use embedding of this area routine to disengage the negative electrode active material of lithium, for example electric conductive polymer, the lamellar compound (material with carbon element, metal oxide etc.) etc. of lithium metal, lithium alloy, lithium doping, described material with carbon element is one or more that are selected from non-graphitic carbon, graphite or the charcoal being 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 by products therefrom after the sintering such as phenolic resins, epoxy resin charing.Wherein, can, by metallic lithium foil as negative active core-shell material and negative pole conducting base, metallic lithium foil directly can be used as to negative pole battery simple for production.
The kind of described negative pole adhesive and content are conventionally known to one of skill in the art, and for example 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, take the weight of negative electrode active material as benchmark, the content of negative pole adhesive is 0.01-10 % by weight, is preferably 0.02-5 % by weight.
Described negative material can also comprise that 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, such as one or more in carbon black, nickel powder, copper powder.Take the weight of negative electrode active material as benchmark, the content of described conductive agent is 0-12 % by weight, is preferably 2-10 % by weight.
Negative pole conducting base can be negative pole conducting base conventional in lithium ion battery, as stamped metal, and metal forming, net metal, foamed metal uses Copper Foil as negative pole conducting base in specific embodiment of the invention scheme.
The preparation method of described negative pole can adopt conventional preparation method, for example, negative electrode active material and binding agent are dissolved according to a certain percentage and in solvent, are mixed into slurries, then on wide cut conducting base, apply this slurries, and then dry, roll-in is also cut, and obtains pole piece.Condition dry and roll-in is known in those skilled in the art, and for example the temperature of dry negative plate is generally 60-120 ℃, preferably 80-110 ℃, and be 0.5-5 hour drying time.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,, take the weight of negative electrode active material as 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, and it is not particularly limited, and 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), tetraphenyl lithium borate (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 is selected 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.
To the present invention be described in more detail by embodiment below.
The various raw materials that use in embodiment are the conventional various raw materials that use in this area, all can be 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) is 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 the aluminium foil that 12 μ m are thick, and then 120 ℃ of dry 5h, then use tablet press machine compressing tablet, finally section, the lithium ion cell positive of grown × wide × thick=551mm × 44mm × 130 μ m.
(2) preparation of anodic aluminium oxide membrane
0.5g polyvinylidene fluoride is stirred and is dissolved in 5gN-methyl pyrrolidone, and adding 8.6g particle diameter is the lithium manganese phosphate powder of 50nm, with electric mixer (speed is 1000rpm) stirring 20min, obtains inorganic slurry, and solid content is controlled at 61wt%.Be coated in above-mentioned anode pole piece surface with coating machine, coating thickness 10 μ m, obtain being coated with the anode pole piece of anodic aluminium oxide membrane after 120 ℃ of dry 5h in vacuum.
The porosity that the full-automatic mercury injection apparatus of Auto pore IV 9500 that adopts Merck & Co., Inc of the U.S. to produce records anodic aluminium oxide membrane is 50%.
The pick up that records anodic aluminium oxide membrane is 55%.
Adopt the above-mentioned anodic aluminium oxide membrane making 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, and is beneficial to lithium ion and passes through.
(3) preparation of battery
The anode pole piece that is attached with anodic aluminium oxide membrane and metal lithium sheet that abovementioned steps (2) is made, 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/L LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is=1: 1).The assembling process of battery is all carried out in the glove box that is full of argon gas.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare battery sample S2, the coating thickness of inorganic slurry that different is is 5 μ m.
The porosity that adopts 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 of inorganic slurry that different is is 20 μ m.
The porosity that adopts 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 of inorganic slurry that different is is 30 μ m.
The porosity that adopts 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 of different is lithium manganese phosphate is 100nm.
The porosity that adopts 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 of different is lithium manganese phosphate is 200nm.
The porosity that adopts 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 of different is lithium manganese phosphate is 3.5g, and the solid content of the inorganic slurry making is 39wt%.
The porosity that adopts the method identical with embodiment 1 to record anodic aluminium oxide membrane is 75%, and pick up is 137%.
Adopt the method identical with embodiment 1 to prepare battery sample S8, the amount of different is lithium manganese phosphate is 31g, and the solid content of the inorganic slurry making is 85wt%.
The porosity that adopts 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) is 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 the aluminium foil that 12 μ m are thick, and then 120 ℃ of dry 5h, then use tablet press machine compressing tablet, finally section, the lithium ion cell positive of grown × wide × thick=551mm × 44mm × 130 μ m.
(2) preparation of anodic aluminium oxide membrane
0.5g polyvinylidene fluoride is stirred and is dissolved in 5gN-methyl pyrrolidone, and adding 9.5g particle diameter is the lithium manganese phosphate powder of 40nm, with electric mixer (speed is 900rpm) stirring 20min, obtains inorganic slurry, and solid content is controlled at 63wt%.Be coated in metal lithium sheet surface with coating machine, coating thickness 10 μ m, obtain being coated with the cathode pole piece of anodic aluminium oxide membrane after 120 ℃ of dry 5h in vacuum.
The porosity that adopts 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 is attached with anodic aluminium oxide membrane that abovementioned steps (2) is made and step (1) make, wherein, is attached with the face of anodic aluminium oxide membrane with anodal staggered relatively, make button cell, then inject 0.05g electrolyte, finally sealed battery case, makes lithium ion battery sample S9.Electrolyte is 1mol/L LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is=1: 1).The assembling process of battery is all carried out in the glove box that is full of argon gas.
Comparative example 1
(1) preparation of positive plate
Take LiFePO4 (LiFePO
4), acetylene black, polyvinylidene fluoride (PVDF), 1-METHYLPYRROLIDONE (NMP) is 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 the aluminium foil that 12 μ m are thick, and then 120 ℃ of dry 5h, then use tablet press machine compressing tablet, finally section, the lithium ion cell positive of grown × wide × thick=551mm × 44mm × 130 μ m.
(2) preparation of anodic aluminium oxide membrane
0.5g polyvinylidene fluoride is stirred and is dissolved in 5gN-methyl pyrrolidone, add 8.6g alumina powder, with electric mixer (speed is 1000rpm) stirring 20min, obtain inorganic slurry, solid content is controlled at 61wt%.Be coated in above-mentioned anode pole piece surface with coating machine, coating thickness 10 μ m, obtain being coated with the anode pole piece of anodic aluminium oxide membrane after 120 ℃ of dry 5h in vacuum.
The porosity that adopts 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 is attached with anodic aluminium oxide membrane and metal lithium sheet that abovementioned steps (2) is made, 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/L LiPF
6ethylene carbonate (EC) and the mixed solution of dimethyl carbonate (DMC) (volume ratio is=1: 1).The assembling process of battery is all carried out in the glove box that is full of argon gas.
Performance test
1, anodic aluminium oxide membrane porosity: the open-cell porosity of anodic aluminium oxide membrane prepared by the full-automatic mercury injection apparatus test above-described embodiment 1-9 of Auto pore IV 9500 that uses Merck & Co., Inc of the U.S. to produce and comparative example 1, maximum pressure is 30000PSI, test result is in table 1.
2, the negative or positive electrode of being prepared by above-described embodiment 1-9 and comparative example 1 soaks 30min in electrolyte, weighs the added value of pole piece weight after taking out, and is labeled as m
1; The positive pole that is attached with anodic aluminium oxide membrane or negative pole prepared by above-described embodiment 1-9 and comparative example 1 soak 30min in electrolyte, weigh the added value of pole piece weight after taking out, and are labeled as m
2; m
2deduct m
1the weight m obtaining
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
The battery S1-S9 that just prepared by embodiment 1-9 and comparative example 1 and DS1 are placed in respectively on computer program-control charge-discharge test instrument and carry out electrochemical property test, and voltage range is 3～4.2V, and charge-discharge magnification is 1C.
It is the de-lithium of work electrode that battery is set to charged state, and the density of charging current is 0.5mA/cm
2, charge to cut-ff voltage out of service, calculate initial charge specific capacity.
De-lithium specific capacity (mAh/g) first=quality of de-lithium capacity/active material first
After de-lithium finishes first, then battery to be set to discharge condition be work electrode embedding lithium, discharge current density is 0.5mA/cm
2, while being discharged to cut-ff voltage, electric discharge finishes, and calculates first discharge specific capacity.
Embedding lithium specific capacity (mAh/g) first=quality of embedding lithium capacity/active material first
Test result is as table 2.
Fig. 2 is charging and discharging curve when 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 carry out respectively loop test, constant current with 0.5mA carries out constant current charge to battery, charge to cut-ff voltage, the same constant current with 0.5mA, to battery constant-current discharge, is discharged to cut-ff voltage, shelves 10 minutes, repeat above step, make continuous charge-discharge test, obtain the battery capacity after 100 circulations of battery, calculate the discharge capacitance of 100 rear batteries of circulation.
Discharge capacity/discharge capacity × 100% first after time circulation of discharge capacitance=100, test result is as table 2.
Security performance: can battery, after 200 ℃ of high-temperature bakings, normally discharge and recharge.
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 |
| |
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 |
100 cyclic discharge capacity conservation rates (%) | After 200 ℃ of bakings, can normally discharge and recharge |
| 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, reels also convenient time prepared by electrode group, can there is not the uneven short circuit phenomenon causing of diaphragm position, can simplify greatly winding process, improve the make efficiency of battery, energy consumption and cost are 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, and nonflammable, 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 modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (18)
1. a lithium ion battery, it is characterized in that, comprise housing and be sealed in electrode group and the electrolyte in housing, 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, with respect 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 anodal surface.
6. battery according to claim 1, is characterized in that, with respect 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 particle average grain diameter of described lithium manganese phosphate is 30-300nm.
8. battery according to claim 1, is characterized in that, the particle average grain diameter 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 μ m.
10. battery according to claim 1, is characterized in that, the thickness of described anodic aluminium oxide membrane is 1 ~ 10 μ m.
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 reel or the stacked electrode group that makes, described anodic aluminium oxide membrane is attached to anodal surface and/or negative terminal surface, described anodic aluminium oxide membrane comprises lithium manganese phosphate and binding agent, with respect 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, added electrolyte, then sealing.
12. preparation methods according to claim 11, is characterized in that, step S1 comprises first anodic aluminium oxide membrane is attached to negative terminal surface, then will be attached with the negative terminal surface and anodal rear coiling staggered relatively or the stacked electrode group that makes of anodic aluminium oxide membrane.
13. preparation methods according to claim 11, is characterized in that, step S1 comprises and first anodic aluminium oxide membrane is attached to anodal surface, then will be attached with the positive pole surface and negative pole rear coiling staggered relatively or the stacked electrode group that makes of anodic aluminium oxide membrane.
14. according to the preparation method described in claim 12 or 13, it is characterized in that, anodic aluminium oxide membrane is attached to anodal surface and comprises that the inorganic slurry that contains lithium manganese phosphate, binding agent and solvent is coated on to anodal surface to be gone up, dry;
Or anodic aluminium oxide membrane is attached to negative terminal surface and comprises the inorganic slurry that contains lithium manganese phosphate, binding agent and solvent is coated in negative terminal surface, dry;
The solid content of described inorganic slurry is 35-85wt%.
15. preparation methods according to claim 14, is characterized in that, described in the thickness that is coated on anodal surface or is coated on negative terminal surface be 1-30 μ m.
16. preparation methods according to claim 14, 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.
17. preparation methods according to claim 14, it is characterized in that, the preparation of described inorganic slurry comprise by lithium manganese phosphate, binding agent and solvent stir condition under mix, the speed of described stirring is 500-1000rpm, the time of described stirring is 5 ~ 60min.
18. preparation methods according to claim 14, is characterized in that, described dry temperature is 60-120 ℃, and be 0.5-24h drying time.
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| WO2019101174A1 (en) * | 2017-11-24 | 2019-05-31 | 比亚迪股份有限公司 | Lithium ion battery separator, manufacturing method therefor, and lithium ion battery comprising the separator |
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