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CN1167164C - Microporous solid electrolytes and methods for preparing them - Google Patents

Microporous solid electrolytes and methods for preparing them Download PDF

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Publication number
CN1167164C
CN1167164C CNB998149195A CN99814919A CN1167164C CN 1167164 C CN1167164 C CN 1167164C CN B998149195 A CNB998149195 A CN B998149195A CN 99814919 A CN99814919 A CN 99814919A CN 1167164 C CN1167164 C CN 1167164C
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solvent
mixture
polymer
electrolyte
dielectric film
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CN1331848A (en
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�Ŷ�ѫ
张东勋
金思钦
金汉俊
洪性珉
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Finecell Co Ltd
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Abstract

The present invention relates to a solid electrolyte having a good conductivity to lithium ion by allowing the liquid components and lithium salts to be absorbed into the electrolyte film containing an absorbent added at the time of its preparation and having a porosity, a process for preparing the same and a rechargeable lithium cell using the same as an electrolyte. As the absorbent, inorganic materials having not more than 40 mu m of particle size can be used. As the polymer binder, any binder of whom solubility against the liquid electrolyte is small can be used. A wet process can introduce the porous structure of the electrolyte film. The solid electrolyte according to the present invention has the ionic conductivity of more than approximately 1 to 3 x 10<-3> S/cm at room temperature and low reactivity to lithium metal. The cell is fabricated from the solid electrolyte together with electrodes by lamination or pressing methods and, the liquid electrolyte, which is decomposed by moisture, is introduced to a cell just before packaging. Therefore, the solid electrolyte according to the present invention is not affected by the humidity and temperature conditions during the manufacturing of the electrolyte film. In addition, the solid electrolyte according to the present invention has high thermal, mechanical and electrochemical stability, and thus is suitable as an electrolyte for rechargeable lithium cells.

Description

Many micropores solid electrolyte and preparation method thereof
Technical field
The present invention relates to a kind of dielectric film that is used for rechargeable battery.More particularly, have multi-cellular structure and contain in the dielectric film of adsorbent by liquid parts and lithium salts (hereinafter being referred to as " liquid electrolyte ") are imported, the mobile passage that provides of ion is provided between negative electrode and anode in the process of rechargeable battery recharge and discharge
Electrochemical cell comprises three piths, i.e. negative electrode, anode and electrolyte.The embodiment of described anode material is the mixture that can add lithium metal or lithium ion, is preferably carbon and polymeric material.The embodiment of described cathode material is the material that can add lithium ion, for example, can use oxide or polymeric material, as lithium and cobalt oxides (Li xCoO 2), lithium nickel oxide (Li xNiO 2), lithium-nickel-cobalt-oxygen thing (Li xNi yCo 1-yO 2), spinel lithium manganese oxide (Li xMn 2O 4) and manganese dioxide (MnO 2).Liquid electrolyte is imported the formation that can cause the ionic conduction matrix in the described dielectric film.
Background technology
Use the electrochemical cell of polymer dielectric to have the following advantages with respect to the battery that uses liquid electrolyte: they are not easy leakage (1); (2) they have good electrochemical stability, and this character makes them can make the battery of different model; They make the automatic control of manufacture method become easy to reach (3).
Interact because the polarity isomery atom that polymer such as polyoxyethylene contain can electricity take place with metal ion, make described polymer have metal ion conductivity, thereby the research of ionic conductive polymer (being polymer dielectric) is carried out energetically.Yet, (be about 10 because straight polymer such as polyoxyethylene at room temperature have very low ionic conductivity -8S/cm), their shortcoming is in order to reach electrochemical cell desired about 10 -4The ionic conductivity of S/cm can only be worked under about 100 ℃ temperature.For this reason, the research to polymer dielectric mainly concentrates on the raising conductivity.
The conduction that it is found that the polymer dielectric intermediate ion needs the transmission of polymer chain, thereby attempts to pass through to increase the flowability of polymer chain to improve the conductivity of ion.People such as Blonsky propose a kind of manufacturing conductivity and increase to 10 -5The electrolytical method of S/cm, this method connects (J.Am.Chem.Soc., 106,6854 (1984)) by introduce phosphonitrile on main polymer chain.Yet said electrolyte still has lower conductivity and relatively poor mechanical strength.
On the other hand, in order to reduce crystallinity of polymer, people attempt by the structure that changes polymer or add inorganic material in polymer.Yet the straight polymer electrolyte of being made up of polymer and slaine (not containing liquid electrolyte) does not still possess enough conductivity.
On the contrary, United States Patent (USP) 5,219,679 disclosed gel-type electrolyte contain liquid electrolyte on its main polymer chain, confirmed to have conductivity near liquid electrolyte, simultaneously their mechanical property has the character of polymer, for the commercialization of rechargeable battery provides may.That is to say, the battery of described patent does not need to add individually the activation process of liquid electrolyte, but combines a certain amount of liquid electrolyte in the process of preparation polymer dielectric (a kind of polymer solution of pressing through casting and the mixture of liquid electrolyte).Yet, United States Patent (USP) 5,219, still there are some problems in 679 electrolyte, because contained polymer (as polyacrylonitrile) can react with the lithium metal, thereby battery deposit and between the operating period product of electrolyte and lithium electrode can accumulate gradually, this causes continuing to increase of interface resistance.
Simultaneously, people such as Scrosati use prepares gel-type polymer electrolyte (Electrochim.Acta, 140,991 (1995)) with the polymethyl methacrylate that the lithium metal has hypoergia.Use polymethyl methacrylate to have hypoergia on the lithium surface, thereby its advantage is that the phenomenon that increases at electrode surface resistance during storage is inhibited as the electrolyte of component of polymer.Yet its shortcoming is that described electrolytical mechanical strength is low, thereby should increase the content of polymer so that its intensity is enough to form film, and this can make conductivity reduce to 10 conversely -4S/cm.In addition, because the gel-type electrolyte contains a large amount of liquid parts, the evaporation of liquid parts can appear inevitably on electrolytical surface.Based on this, the evaporation of liquid parts can change composition in depositing process, and this can make conductivity reduce.In addition, it is to need dewatered atmosphere that this method has a shortcoming, and wherein moisture will be removed to minimum content because in the liquid electrolyte contained lithium salts can and air in reaction of moisture and decompose.
United States Patent (USP) 5,296,318 and 5,418,091 provides a kind of polymer dielectric system of mixing to remedy said deficiency.Before the parcel battery, be subject to the liquid electrolyte of moisture effects by adding, (gel-type polymer electrolyte contains a large amount of liquid electrolytes to have utilized the advantage of gel-type polymer electrolyte simultaneously, conductivity of lithium ions is undertaken by liquid phase, thereby have a conductivity similar with liquid electrolyte), the polymer electrolytic mass-energy of described mixing reduces to minimum with moisture to the influence of electrolyte preparation method.Yet,, should have the position that can adsorb liquid parts or have the active force that can penetrate liquid parts in the inside of dielectric film because dielectric film has added liquid electrolyte after being produced.At last, in the step of preparation dielectric film, add dibutyl phthalate, after the assembling of battery is finished, with an organic solvent enter the position of energy adsorptive liquid composition and separate plasticizer as alcohol or ether as plasticizer.Yet, using chemical reaction to separate in the process of repefral, the shortcoming of this method is that recyclability is low, it is difficult to control automatically when output decline reaches a large amount of production.
Therefore, the present inventor makes great efforts to solve above-mentioned deficiency of the prior art in korean patent application 98-57030, can adsorb liquid electrolytical adsorbent by in the polymeric matrix body, adding, after the battery assembling, in the activation process of battery, introduce liquid electrolyte.
The dielectric film of described solid electrolyte is made under drying condition by adsorbent and polymer adhesive.The density structure of polymer adhesive is changeable.In order to show better lithium ion conductivity by the adsorption capacity that improves liquid electrolyte, the solid electrolyte that needs the stereochemical structure of dielectric film to change simultaneously.
Detailed Description Of The Invention
Therefore, the present invention makes great efforts to solve the deficiency among the preparation method of above-mentioned solid electrolyte, is included in to add in polymeric matrix after the battery assembling can adsorb liquid electrolytical adsorbent with the formation dielectric film.That is to say that the present invention makes polymeric matrix produce microcellular structure, keeps the mechanical strength of dielectric film itself simultaneously, this had both helped adsorption liquid attitude electrolyte, had improved the conductivity of lithium ion in the solid electrolyte again.
Used term " dielectric film " refers to system dielectric film that be engaged in and don't that contain any liquid electrolyte under drying condition in the specification.Term in the specification " solid electrolyte " refers to said by have the dielectric film of ionic conductivity in conjunction with liquid electrolyte.Though solid electrolyte because contain liquid electrolyte rather than be in fully solid-state, for liquid electrolyte with show the difference be " solid electrolyte " because the basic framework of the contained solid electrolyte of dielectric film is in solid state.In addition, used term " adsorbent " refers to adsorb liquid electrolytical material and maybe can increase the material that solid electrolyte adsorbs liquid electrolytical ability in the specification.
The method of finished product battery refers to the method for combined with cathode and anode, and negative electrode and anode are prepared separately respectively, is inserted through the dielectric film that rolls or push formation between negative electrode and the anode.When dielectric film prepares by one of described method, in the battery that has assembled, add liquid electrolyte, this can minimize the restriction to moistureproof condition in the described method.In addition, the method according to this invention can be adsorbed liquid electrolytical position and just form in the process of preparation dielectric film, thereby no longer be needed to separate the step of plasticizer.Thereby the advantage of described method is to simplify the operation, and this has not only reduced manufacturing cost, and automatic operation is become easily and has improved output.In addition, when by one of wherein said method preparation dielectric film, polymeric matrix begins to form multi-cellular structure, and this helps the transmission of liquid electrolyte, has improved the lithium ion conductivity of the solid electrolyte of the adsorbent with same quantity conversely again.
Solid electrolyte of the present invention comprises a kind of dielectric film and a kind of liquid electrolyte with ionic conductivity of being formed and contained inorganic adsorbent by multi-cellular structure.
In the present invention, be used for the solid electrolyte of rechargeable battery, comprise: thickness is 10-200 μ m and the dielectric film with microcellular structure; And percentage by weight is the liquid electrolyte with ionic conductivity of 30-90%, described weight is based on the electrolytical gross weight that comprises liquid electrolyte, wherein said dielectric film contains the adsorbent that particle size is no more than 40 μ m, its content is 30-95% with respect to the gross weight of the dry state dielectric film that does not contain liquid electrolyte by weight, wherein said adsorbent is the mixture that is selected from a kind of particle in following group or two or more particles, and described group comprises porous polymer particles, mineral grain, composite oxide particle, the aperture of being made by oxide or polymer material is particle and other commercially available adsorbents of the mesoporous molecular sieve of 2-30nm; The liquid electrolyte of described ionic conductivity is dissolved in by the lithium salts with one or more in mixture of one or more organic solvents and obtains.
A kind of chargeable lithium cell, make by following step: the mixture of dissolving adsorbent and polymer adhesive in a kind of solvent that is applicable to polymer adhesive, make resulting solution change film forming, exchange described solvent with a kind of non-solvent of polymer adhesive that is applicable to, dry resulting material forms the many micropores dielectric film that contains adsorbent, with negative electrode and anode the be assembled together formation battery of prepared dielectric film with preparation respectively, and make liquid electrolyte that the absorption of resulting battery has an ionic conductivity wherein then, described adsorbent is the mixture that is selected from a kind of particle in following group or two or more particles, and described group comprises porous polymer particles, mineral grain, composite oxide particle, the aperture of being made by oxide or polymer material is particle and other commercially available adsorbents of the mesoporous molecular sieve of 2-30nm; The liquid electrolyte of described ionic conductivity is dissolved in by the lithium salts with one or more in mixture of one or more organic solvents and obtains; Described polymer adhesive is to be selected from following group one or more mixture, described group comprises: poly-inclined to one side 1, the 1-difluoroethylene, 1, the copolymer of 1-difluoroethylene and hexafluoropropylene, 1, the copolymer of 1-difluoroethylene and maleic anhydride, polyvinyl chloride, polymethyl methacrylate, polymethacrylates, cellulose triacetate, polyurethanes, polysulfones, polyethers, polyethylene, polypropylene, poly(ethylene oxide), polyisobutene, polybutadiene, polyvinyl alcohol, polyacrylonitrile, polyimides, polyvinyl formal, acrylonitrile butadiene rubber, ethylene-propylene-diene-monomer, four (ethene glycol), two propylene esters, dimethyl silicone polymer, Merlon and silicon polymer, or their copolymer; The solvent of dissolve polymer adhesive is the mixture that is selected from following group one or both or multiple solvent composition, and described group comprises: N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, oxolane, acetonitrile, cyclohexanone, chloroform, carrene, hexamethyl phosphoramide, methyl-sulfoxide, acetone and dioxane; And the non-solvent that is used for polymer adhesive is one or both or the multiple mixture of being made up of following substances, and described material is selected from: water, ethanol, ethylene glycol, glycerol, acetone, carrene, ethyl acetate, butanols, amylalcohol, hexanol and ether.
Said dielectric film is preferably the method preparation by phase transformation.The embodiment of this method comprises wet method and dry method.Wet method refers to a kind of method for preparing dielectric film, may further comprise the steps:
The mixture of dissolving adsorbent and polymer adhesive in a kind of solvent that is applicable to polymer adhesive,
Make resulting solution be transformed into form membrane,
Exchange described solvent with a kind of non-solvent of polymer adhesive that is applicable to, and
Dry resulting material forms dielectric film.
On the contrary, dry method refers to a kind of method for preparing dielectric film, comprises the steps:
With the mixture of adsorbent and polymer adhesive and solvent that can the dissolve polymer adhesive, can not the dissolve polymer adhesive non-solvent, pore-forming agent and wetting agent mix mutually,
Make resulting mixture form form membrane, and
The resulting film of intensive drying.
Ensuing activation process (liquid electrolyte that will have ionic conductivity is introduced in the prepared porous electrolyte film) can make the solid electrolyte that is used for rechargeable battery.
Therefore, solid electrolyte of the present invention can prepare in the following way: can adsorb liquid electrolyte or increase inside that the adsorbent of adsorption capacity imports dielectric film to form porous electrolyte film matrix, and embed liquid electrolyte then in described hole.Like this Zhi Bei solid electrolyte at room temperature lithium ion conductivity be about 1-3 * 10 -3S/cm.
The embodiment that can adsorb the adsorbent of liquid electrolyte or increase adsorption capacity comprises organic material such as porous polymer and inorganic material such as mineral grain.
As for the porous polymer adsorbent, can use polypropylene, polyethylene, polystyrene and polyurethanes, the formation in hole is to be imported into the network polymers of side chain or by adjusting the parameter of the method according to this invention by big molecule functional group.Also can use natural polymer, as wood chip, paper pulp and cork.
As for inorganic adsorbent, can use one or both or the multiple particle that is selected from mineral grain, composite oxide particle and mesoporous molecular sieve.The embodiment of said mineral grain comprises the mineral grain with phyllosilicate structures, as clay, paragonite, montmorillonite and mica.The embodiment of described composite oxide particle comprises zeolite, porous silica and Woelm Alumina.The embodiment of central hole structure molecular sieve comprises that the aperture is the mesoporous molecular sieve of being made by oxide such as silicon/polymer material of 2-30nm.Said mineral grain, composite oxides and mesoporous molecular sieve can be mixed together use, and wherein the adsorbent mentioned above being selected from of two or more adsorbents is used in combination.
Said inorganic adsorbent has mechanical strength stability, thermal stability and electrochemical stability preferably with respect to organic adsorbent (as porous polymer), thereby the performance of the rechargeable battery of use inorganic adsorbent is better than the performance of the rechargeable battery that uses organic adsorbent.
That is to say, during by extruding or laminating method assembling anode and negative electrode making battery, the mechanical strength of organic adsorbent and thermal stability are different from the dielectric film or the polymer adhesive of combination electrode, thereby use the rechargeable battery of described organic adsorbent significantly to reduce with respect to rechargeable battery discharge capacity in the process of recharge and discharge of using inorganic adsorbent.For example, the adsorbent of being made up of organic material (as the polymer of low melting point or inferior mechanical intensity) can lose adsorption capacity in the process of extruding or lamination.In other words, use organic adsorbent (as polymer) to have the performance that is beneficial to dielectric film or solid electrolyte itself, but when making battery, be difficult to keep their initial performance by extruding or laminating method.
In addition, explained above resembling that because the electrolytical ionic conductivity of the direct impact polymer of transmission of polymer chain, temperature is very important to the influence of ionic conductivity.Specifically, at low temperatures, the transmission of polymer chain is weakened, and this has reduced the conductivity of ion widely, thereby makes the degradation of made battery.Yet adsorbent used in the present invention has increased the conductivity of ion.In addition, if use the not inorganic adsorbent of temperature influence in a large number, Temperature Influence will reduce, and this is different from the electrolytical character of general polymerization thing.Because contain a large amount of inorganic adsorbents in the electrolyte, its advantage is to have improved fire resistance and anti-knock properties with respect to the electrolyte that contains a large amount of organic materials (as polymer).
Therefore, preferred inorganic adsorbent rather than the organic adsorbent of using in the composition of the dielectric film of rechargeable battery.
The adsorbent that is added is 30-95% with respect to the dry state dielectric film that does not contain liquid electrolyte by weight, is preferably 50-90%.If the amount that is added surpasses 95% (weight), the mechanical strength of prepared dielectric film reduces.If addition is no more than 30% (weight), dielectric film adsorbs liquid electrolytical ability to be reduced.
The particle size of adsorbent is preferably and is no more than 40 μ m, more preferably is no more than 20 μ m, thereby does not reduce the mechanical strength and the uniformity of dielectric film.
As for polymer adhesive, can use the most frequently used polymer.Between them, preferred one or both or multiple being selected from: poly-inclined to one side 1 by following substances, the 1-difluoroethylene, 1, the copolymer of 1-difluoroethylene and hexafluoropropylene, 1, the copolymer of 1-difluoroethylene and maleic anhydride, polyvinyl chloride, polymethyl methacrylate, polymethacrylates, cellulose triacetate, polyurethanes, polysulfones, polyethers, polyolefin (as polyethylene or polypropylene), poly(ethylene oxide), polyisobutene, polybutadiene (polybutyldiene), polyvinyl alcohol, polyacrylonitrile, polyimides, polyvinyl formal, acrylonitrile butadiene (acrylonitrilebutyldiene) rubber, ethylene-propylene-diene-monomer, four (ethene glycol), two propylene esters, dimethyl silicone polymer, Merlon and silicon polymer, or their copolymer.
The present invention introduces loose structure as in the dielectric film of solid electrolyte matrix, and this helps the transmission of liquid electrolyte, thereby uses the adsorbent of same quantity to improve the lithium ion conductivity of solid electrolyte.The method for preparing said porous electrolyte film as mentioned above comprises wet method and dry method.The operation of wet method is that the dielectric film composition is carried out mold, then resulting film and non-solvent is reacted to form microcellular structure on polymeric matrix.Dry method operation be with the dielectric film composition with the non-solvent that is used for manufacturing hole and pore-forming agent moulding to form microporous dielectric film.
For the solvent of dissolve polymer adhesive, by the mixture of one or both or multiple solvent composition, described solvent is selected from following material: N-methyl pyrrolidone (N-methylpyrrolidinone), dimethyl formamide, dimethylacetylamide, oxolane, acetonitrile, cyclohexanone, chloroform, carrene, hexamethyl phosphoramide, methyl-sulfoxide, acetone and dioxane.
For the non-solvent that is used for polymer adhesive, can use one or both or the multiple mixture of being made up of following substances, described material is selected from: water, ethanol, ethylene glycol, glycerol, acetone, carrene, ethyl acetate, butanols, amylalcohol, hexanol and ether.
As for pore-forming agent, the preferred mixture of being made up of following one or both or multiple material that uses, described material is selected from: 2-propyl alcohol, resorcinol, trifluoroethanol, cyclohexanol, hexafluoroisopropanol, methyl alcohol and react the hemiacetal that makes by maleic acid and Hexafluoro acetone.
As for impregnating agent, preferably use non-ionic surface active agent, for example, Triton X-100 (making), Igepal DM-710 (making) by GAF company by Aldrich company.
The liquid electrolyte that contains adsorbent will be dissolved in the dielectric film, and described liquid electrolyte can make by the method for dissolving lithium salts in organic solvent.In the present invention, liquid electrolyte is adsorbed in the dielectric film and is defined as " activation ".
Described organic solvent be preferably strong polarity and and the lithium metal do not have reactive solvent, to improve the degree of dissociation of ion and to be beneficial to the mobile of ion by the local viscosity that reduces around the ion by improving electrolytical polarity.The embodiment of this organic solvent comprises ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid Methylethyl ester, gamma-butyrolacton, methyl-sulfoxide, 1,3-dioxane, oxolane, 2-methyltetrahydrofuran, sulfolane, N, dinethylformamide, diethylene glycol dimethyl ether, triglyme and tetraethylene glycol dimethyl ether.Specifically, organic solvent is preferably the mixed liquor of two or more solvents, and described solvent is made up of high viscosity solvent and low viscosity solvent.
Said lithium salts is preferably the lithium salts with low lattice energy and high degree of dissociation.The embodiment of this lithium salts comprises LiClO 4, LiBF 4, LiPF 6, LiAsF 6, LiSCN, LICF 3SO 3, LiN (CF 3SO 2) 2And LiC (CF 3SO 2) 3Can select mixture wherein.The concentration of lithium salts is preferably 0.5M-2M.
The amount of the liquid electrolyte that is added is 30-90% (weight) based on the electrolytical gross weight that comprises liquid electrolyte, is preferably 40-85% (weight).
Solid electrolyte according to the present invention is characterised in that it prepares easily with respect to existing polymer dielectric; Because the conduction of lithium ion is undertaken by liquid phase, described solid electrolyte has higher ionic conductivity; And be not subjected to moisture or Temperature Influence, adsorbed liquid electrolyte or be activated up to described solid electrolyte.
Hereinafter, the preparation method to the solid electrolyte of described loose structure makes more detailed description.
Wet method
Can be according to porous solid electrolyte of the present invention by the preparation of five steps, i.e. mixed adsorbent and polymer adhesive dissolve resulting mixture, moulding, make main polymer chain and drying/activation.
At first, Powdered adsorbent (particle diameter is no more than 40 microns) and polymer adhesive dry mixed in the container of sealing.
The mixture of resulting adsorbent and polymer adhesive is dissolved in the solvent that is suitable for polymer adhesive.Solids content is preferably 5-50% with respect to the solution gross weight in the described mixed liquor.If described content is no more than 5% (weight), then the mechanical strength of dielectric film can reduce, if described content surpasses 50%, then polymer adhesive can not fully be dissolved, and perhaps the viscosity of mixed solution becomes big, and this all is disadvantageous.
For the dissolving that promotes polymer adhesive and avoid the adsorbent caking, mix liquid with magnetic stirring apparatus, mechanical agitator, planet strrier or high-speed dispersion mixer.When stirring, can use the ultrasonic agitation device to prevent adsorbent caking or foaming when mixing.In addition, if necessary, can carry out de-bubble and filtration treatment to mixed liquor.
Polymer adhesive dissolve fully and and adsorbent evenly after the mixing, resulting mixture is made with the film of uniform thickness.For example, can be cast in mixed liquor on the plate glass or the teflon dish on, cast pressure then to obtain the product of uniform thickness.On the other hand, mixed liquor can also be separated from the mould of rule space, coats then in the substrate of being made up of polymer film.Can select the disclosed distinct methods of other patent applications.The thickness of film is preferably and is controlled between the 10-200 μ m.If the thickness of film is no more than 10 μ m, mechanical strength can reduce, and if the thickness of film surpasses 200 μ m, the conductivity of ion can reduce, this all is disadvantageous.
After the casting of described mixture is pressed into film, produce porous in the polymeric matrix, described film and be applicable to that the non-solvent of polymer adhesive contacts to separate the solvent that is applicable to polymer adhesive in order to make.For example, can separate described solvent by in containing the non-solvent pond of non-solvent, soaking described film.Therefore, being preferably easy miscible agent mixes mutually with non-solvent.The time of soaking film in the non-solvent pond, its time changed the kind that depends on solvent and non-solvent from 1 minute to 1 hour.If the time is shorter than official hour, be difficult to obtain enough holes.On the contrary, if the time exceeds schedule time, output then can reduce, and this all is disadvantageous.The temperature in described pond is preferably 10 ℃-90 ℃, more preferably 20 ℃-80 ℃.If temperature is lower than described temperature, then be difficult to obtain enough holes.If temperature is too high, the mechanical strength of dielectric film can reduce, and this is not preferred.Generally, preferably according to the porosity that decides generation by the quantity of solvent in the mixed solution of adsorbent, polymer adhesive and solvent composition.Preferably control the time that composition, temperature and solution mix, thereby determine porosity according to the quantity of solvent in the mixed liquor.
Isolate after the resulting film of solvent and bone dry, in described film, import liquid electrolyte.
Dry method
The dry process of loose structure solid electrolyte by being made up of 4 steps is about to adsorbent and mixes, adds additive (solvent, non-solvent, pore-forming agent, impregnating agent) with polymer adhesive mutually according to the present invention, and casting is pressed and drying/activation.
Powdered adsorbent (particle diameter is no more than 40 microns) and polymer adhesive be dry mixed in the container of sealing.The mixture of resulting adsorbent and polymer adhesive is dissolved in the solvent that is applicable to polymer adhesive.
For the dissolving that promotes polymer adhesive and avoid the adsorbent caking, mix liquid with magnetic stirring apparatus, mechanical agitator, planet strrier or high-speed dispersion mixer.When stirring, can use the ultrasonic agitation device to prevent adsorbent caking or foaming when mixing.In addition, if necessary, can carry out de-bubble and filtration step processing to mixed liquor.
Polymer adhesive dissolve fully and and after adsorbent evenly mixes, add a kind of solvent that can not the dissolve polymer adhesive, promptly add a certain amount of non-solvent that polymer adhesive is precipitated.In order to help forming microcellular structure, preferably add pore-forming agent and impregnating agent.After the described mixture that has added additive dissolved fully, resulting mixture was moulded to the film of uniform thickness.For example, can be cast in mixed liquor on the plate glass or the teflon dish on, cast pressure then to obtain the product of uniform thickness.Mixed liquor can be separated from the mould of rule space, is coated in then in the substrate of being made up of polymer film.In addition, can select the disclosed distinct methods of other patent applications.The thickness of film is preferably and is controlled between the 10-200 μ m.If the thickness of film is no more than 10 μ m, mechanical strength can reduce, and if the thickness of film surpasses 200 μ m, the conductivity of ion can reduce, this is not preferred.
After the moulding of film completed, resulting dielectric film was at 20 ℃ of-200 ℃ of bone dries, then to wherein adding liquid electrolyte.
Compare with wet method, dispersion that a shortcoming of dry method is adsorbent, polymer adhesive and additive or mixing ratio be difficulty.In the time can not disperseing completely or mix, (1) dry method be difficult to finish the even dispersion of hole or adsorbent, and (2) are not easy that the dielectric film casting is pressed into shape and (3) mechanical strength and reproducibility and reduce.That is to say that if hole or adsorbent can not evenly disperse, can confirm (1) when dielectric film is used as the electrolyte of electrochemical cell, uneven local state appears in cell reaction; (2) the die casting moulding difficulty of film; And the reduction of (3) mechanical strength, these unfavorable factors have limited the use of dry method.
In addition, dry method need add nonsolvent additive forming the hole, and according to the principle of dry method, solvent should be evaporated (doing) to form the hole before non-solvent adds.If non-solvent was evaporated, then can not form the hole before solvent evaporation.At this point, non-solvent should have fixedness or its boiling point is higher than solvent.Based on this, the problem that dry method exists is the residual non-solvent that has.In other words, boiling point height or the nonvolatile non-solvent than solvent is difficult to remove from dielectric film fully in dry run.Thereby also need a separating step (for example, separate or increase baking temperature) to enough height with alcohol or ether in order to remove non-solvent fully.In addition, because described non-solvent chemical property and electrochemical properties instability,, in the recharge of battery and discharge process, may cause oxidation reaction or reduction reaction if described non-solvent is still stayed in the dielectric film.The performance of battery reduces as a result, descends or gas evaporation occurs as battery capacity.Same problem also appears at other additive except that non-solvent.Because the dielectric film that will prepare just is made up of adsorbent and polymer adhesive, need remove additive or similar substance fully, cause this method comparatively complicated, thereby the reappearance of this technology is relatively poor.
Therefore, preferably prepare dielectric film or solid electrolyte rather than pass through dry method by wet method.
The present invention relates to rechargeable battery, relate in particular to charged lithium cells, wherein said porous solid electrolyte is as electrolyte.
The process of finished product battery refers to combined with cathode and anode, and described negative electrode and anode are prepared separately, the middle dielectric film that forms with lamination, extruding or canoe that inserts.When dielectric film prepares with one of described method, add liquid electrolyte after the battery assembling, this can make this method that the restriction that removes the moisture atmosphere is reduced to minimum.In addition, according to the present invention, can adsorb liquid electrolytical position and in the process of preparation dielectric film, just form, thereby no longer need to separate the process of plasticizer.Thereby, owing to described method has been simplified operating process and has been had following advantage: reduced operating cost, be easy to operate automatically and improved output.In addition, when preparing dielectric film by described method, formed multi-cellular structure on polymeric matrix, the transmission that this helps liquid electrolyte has improved the lithium ion conductive of the solid electrolyte with same quantity.
By using according to solid electrolyte of the present invention, combined with cathode and anode insert the porous electrolyte film by method for preparing in an embodiment of the method that is used for preparing rechargeable battery, and such battery just can complete.This porous electrolyte film contains absorbent powder and has loose structure, is beneficial to adsorb liquid electrolyte.Cathodic electricity is connected on the cathode collector, and anode is connected electrically on the anode collector.Can adsorb liquid electrolyte after this assembling is activated, thereby just make an operable electrochemical cell.
Fig. 1 is shown as the sectional view of rechargeable battery, has wherein used according to solid electrolyte of the present invention.Solid electrolyte (1) contains absorbent powder (11) and liquid electrolyte, and liquid electrolyte is adsorbed in activation process.Negative electrode (2) and cathode collector (22) are electrically connected, and anode (3) and anode collector (33) are electrically connected.
The method for preparing negative electrode and anode is as follows.Negative electrode or anode are made up of a current-collector and a kind of active material layer.Active material layer comprises active material, electric conducting material and adhesive etc.In addition, can add different additives for the performance that improves battery.The current-collector that negative electrode or anode comprised, electric conducting material, adhesive and additive can be identical or different, and this depends on the target that will reach.
Current-collector provides movable passageway for the electronics that produces in the oxidation/reduction reaction, and described negative electrode or the anode of being reflected at takes place.Can adopt common stereotype, paper tinsel, punching press paper tinsel and etched foil etc. as for current-collector, it depends on the performance and the manufacture method of battery.Use stereotype can increase the filling speed of active material, but also make manufacture method become complicated simultaneously.Use paper tinsel can improve the performance of battery and simplify manufacturing process, but it can reduce the compactness of active material.Copper, aluminium, nickel, titanium, stainless steel, carbon etc. can be used as current-collector.Usually, aluminium is used as negative electrode, and copper is used as anode.
Active material is a most important composition in the electrochemical cell, because they have determined the performance of battery, because the charge/discharge of battery (or oxidation/reduction reaction) occurs on these materials.In addition, active material occupies maximum level on active material layer.As for active material of cathode, can use the oxide of transition metal or sulfide, organic compound, polymer compound etc.Preferred oxide or the polymeric material of using is as lithium and cobalt oxides (Li xCoO 2), lithium nickel oxide (Li xNiO 2), lithium-nickel-cobalt-oxygen thing (Li xNi yCo 1-yO 2), spinel lithium manganese oxide (Li xMn 2O 4) and manganese dioxide (MnO 2) etc.As for active material of positive electrode, can use oxide or sulphur compound, organic compound or the polymer of alkali metal, alkaline-earth metal, carbon, filtering metal, preferred carbon or polymeric material.It is very important that target capabilities when using according to battery is selected active material.
Electric conducting material refers to add for the conductivity that improves electronics the material of negative electrode or anode, generally is carbon.Between them, the preferred graphite of electric conducting material, coke, activated carbon and carbon black, more preferably graphite and carbon black.Can from above-mentioned group, select one or both or multiple material for use, and no matter they are synthetic material or natural material.The electric conducting material that adds is 3-15% (weight) with respect to the gross weight of electrolysis material.If the gross weight of the electric conducting material that adds is no more than 3% (weight), conductivity descends, and produces superpotential problem.If described weight has surpassed 15% (weight), the energy density of per unit volume descends, and the side reaction of electric conducting material has aggravated.
Adhesive refers to that the composition that is added can improve the bond properties of active material, is generally polymer.Employed polymer can be used as adhesive in the preparation solid polymer membrane.Adhesive is preferably with the same polymer of dielectric film or have the polymer of miscibility.The adhesive that is added is 15% or still less (weight) with respect to the gross weight of electrolysis material.If adhesive consumption is less than aequum, the bond properties of electrode reduces.If the content of adhesive surpasses 15% (weight), the processing characteristics of electrode and porosity descend.
Additive refers to that the material that is added can improve the performance of battery or electrode, and it can be selected in wide region according to target capabilities or purposes.The additive that is added can improve the bond properties of composite electrode inside or current-collector, cause the porousness or the amorphism of composite electrode, improve the dispersibility of composite electrode composition material, prevent that active material from overcharging/over-discharge can, the reorganization or remove said product, perhaps improve the absorption property of liquid electrolyte.Usually, salt, organic/inorganic compound, mineral matter and polymer can be used as additive, also can select to add the adsorbent of dielectric film.
According to the present invention charged lithium cells is illustrated in greater detail below.
Be in the porous electrolyte film under the dry solid conditions and negative electrode that makes respectively and anode assembling formation battery by what said method (not importing the step of liquid electrolyte) made, liquid electrolyte is adsorbed with the formation charged lithium cells by dielectric film.In order to make used solid electrolyte have enough ionic conductivities, solid electrolyte should be through activation step with the absorption liquid electrolyte.By activation step, solid electrolyte can be used as electrochemical cell and uses.If the obstructed overactivation step of solid electrolyte, the ionic conductivity under the room temperature can reduce significantly, and this is unfavorable for that solid electrolyte itself uses as electrode.
As follows with the preparation method of the negative electrode of described dielectric film assembling and/or anode.Every kind of mixture of cathode material or anode material is kneaded into paste.Resulting paste forms film by casting pressure, coating and screen printing, and resulting film and current-collector combine, and the mode by extruding or lamination forms negative electrode and/or anode.In addition, paste also can be applied directly to and form negative electrode and/or anode on the current-collector.
Directly be used in by the solid electrolyte paste of adsorbent, polymer adhesive and solvent composition on the surface of the electrode that makes by said method to form battery, dielectric film forms on electrode in described battery.Also can form battery by electrode and dielectric film that lamination or extruding make respectively.When by the method for preparing battery, the bonding force between electrode and the dielectric film can increase.Yet, when electrode and dielectric film do not match mutually, perhaps in its preparation process, during the contaminated easily or loss of performance of electrode or dielectric film, be difficult to adopt a kind of method in front.In addition, if during by the dry process dielectric film, electrode may be polluted by non-solvent or pore-forming agent (being used to cause pore structure), this is disadvantageous, specifically, and when water is used as non-solvent or pore-forming agent, anhydrate if can not remove fully by drying steps, the performance of battery can descend.In addition, also having a problem is to be difficult to reach drying condition completely.In a kind of in the back method, though shortcoming be between electrode and the dielectric film bonding force a little less than, its advantage is more obvious, has simplified quality control, technological design and use equipment.Thereby the method for back is better than the method for front.
Dielectric film by method preparation of the present invention contains adsorbent, and its advantage is to have higher mechanical strength with respect to pure dielectric film or other dielectric film that contains gel-type polymer electrolyte or plasticizer.Therefore and since dielectric film of the present invention the extruding or lamination process in metamorphosis little, its advantage be can make on a large scale and defect rate low.That is to say that the dielectric film for preparing by the inventive method has the advantage of extruding of being applicable to or lamination, this more helps quality control, technological design and lectotype selection.
Brief description of drawings
Fig. 1 is the sectional view of a battery, wherein uses electrolyte of the present invention.
Fig. 2 is the curve chart of a linear sweep voltammetry measurement result, detects the electrochemical stability of solid electrolyte of the present invention.
Fig. 3 is the variation of battery discharge capacity in recharge and discharge process, and the battery that wherein comprises the solid electrolyte of inorganic adsorbent is compared with the battery that uses polymer absorbant.
Label declaration in the accompanying drawing
1: solid electrolyte 11: absorbent powder
2: negative electrode 22: cathode collector
3: anode 33: anode collector
Inventive embodiments
In the present invention, according to solid electrolyte of the present invention and use described solid electrolyte to prepare the method for battery details are as follows.At first, carry out the preparation and the Performance Detection of solid electrolyte.In addition, solid electrolyte and anode and the negative electrode formation battery that is assembled together is described the process that battery performance detects then.But the present invention is not limited to these embodiment, and different distortion drop within protection scope of the present invention equally.
Embodiment 1 (wet method)
Adsorbent and PVdF powder are loaded in 20 milliliters of vials, mix 5 minutes with magnetic stirrer under dry state.In resulting mixture, add 4 milliliters of N-methyl pyrrolidones, continue then to stir and dissolve fully up to adhesive.In order to prevent to lump between the adhesive particle, resulting solution is accepted 30 minutes ultrasonic agitation when stirring.Prepared mixed liquor is painted 100 microns thickness on glass plate.Be coated with rete and in non-solvent is bathed, soaked about 10 minutes, then from separate in non-solvent is bathed and 40 ℃ dry 1 hour down.The porous electrolyte film that makes like this soaked in electrolyte about 10 minutes.After liquid electrolyte was adsorbed fully, the variation of weight was determined.Can measure ionic conductivity by using AC impedence method (alternate currentimpedance method).
Table 1 has been summarized the kind of adsorbent and adhesive, the electrolytical character of porous solid: capacity and conductivity.Adsorb liquid electrolytical ability, adsorption capacity (Δ in order to compare the porous solid electrolyte Ab) press following formula definition:
Δ Ab=(amount of adsorbed liquid electrolyte (mg))/(weight of dielectric film (mg))
Table 1
Embodiment Adsorbent PVdF Non-solvent Liquid electrolyte Δ ab Ionic conductivity mS/cm Mechanical strength
Kind Gram Gram
a Paragonite 0.13 0.28 H 2O EC/DMC 1M LiPF 6 7.0 2.1 Excellent
b Paragonite 0.17 0.26 H 2O EC/DMC 1M LiPF 6 6.8 2.2 Excellent
c Paragonite 0.72 0.24 H 2O EC/PC 1M LiPF 6 6.9 1.9 Excellent
d Paragonite 1.06 0.26 H 2O EC/PC 1M LiPF 6 7.5 1.8 Excellent
e Paragonite 1.51 0.26 H 2O EC/DMC 1M LiPF 6 8.0 2.4 Excellent
f Paragonite 2.00 0.26 H 2O EC/DMC 1M LiPF 6 8.5 2.5 Excellent
g Paragonite 1.98 0.25 Ethanol EC/DMC 1M LiPF 6 5.1 1.0 Excellent
h Zeolite 1.37 0.60 H 2O EC/DMC 1M LiPF 6 7.2 1.9 Excellent
i Zeolite 1.50 0.38 H 2O EC/DMC 1M LiPF 6 8.2 2.0 Excellent
j Zeolite 1.65 0.29 H 2O EC/DMC 1M LiPF 6 8.0 2.4 Excellent
k Montmorillonite 1.34 0.58 H 2O EC/DMC 1M LiPF 6 8.0 2.8 Excellent
l Montmorillonite 1.50 0.38 H 2O EC/DMC 1M LiPF 6 8.2 2.9 Excellent
m Porous silica 1.35 0.59 H 2O EC/DMC 1M LiPF 6 8.5 2.4 Excellent
n Polypropylene 1.35 0.60 H 2O EC/DMC 1M LiPF 6 7.0 1.9 Excellent
o Wood chip 1.35 0.60 H 2O EC/DMC 1M LiPF 6 7.4 2.0 Excellent
Embodiment 2 (wet method)
Paragonite powder and binder powders are loaded in 20 milliliters of vials, mix 5 minutes with magnetic stirrer under dry state.In resulting mixture, add 4 milliliters of N-methyl pyrrolidones, continue then to stir and dissolve fully up to adhesive.In order to prevent to lump between the absorbent particles, resulting solution is accepted 30 minutes ultrasonic agitation when stirring.Prepared mixed liquor is painted 100 microns thickness on glass plate.Be coated with rete and in water-bath, soaked about 10 minutes, separate in the water-bath then and 40 ℃ dry about 1 hour down.The porous electrolyte film that makes like this soaked in electrolyte about 10 minutes.After liquid electrolyte was adsorbed fully, the variation of weight was determined.Can measure ionic conductivity by using AC impedence method.The result is as shown in table 2.
Table 2
Embodiment Paragonite Adhesive Liquid electrolyte Δ ab Ionic conductivity mS/cm Mechanical strength
Gram Kind Gram
a 1.98 PVdF 0.24 EC/DMC 1M LiPF 6 8.1 2.4 Excellent
b 2.00 P(VdF-HFP) 0.26 EC/DMC 1M LiPF 6 8.0 2.6 Excellent
c 1.95 PAN 0.25 EC/DMC 1M LiPF 6 7.8 2.2 Excellent
d 2.00 PU 0.26 EC/DMC 1M LiPF 6 8.9 2.9 Excellent
e 1.98 PVC 0.25 EC/DMC 1M LiPF 6 7.4 2.0 Excellent
f 2.00 P(VdF-HFP) 0.26 EC/DMC 1M LiPF 6 8.5 2.5 Excellent
Embodiment 3 (dry method)
1.17 gram paragonite and 0.5 gram P (VdF-HFP) powder are loaded in 20 milliliters of vials, mix 5 minutes with magnetic stirrer under dry state.In resulting mixture, add 8 gram acetone, continue then to stir to dissolve fully up to adhesive.In order to prevent to lump between the adhesive particle, resulting solution is accepted 30 minutes ultrasonic agitation when stirring.In resulting mixed liquor, add 0.9 gram ethylene glycol, 0.1 gram Triton X-100 and 1.8 gram isopropyl alcohols, then about 10 minutes mixtures up to adding of resulting mixed liquor ultrasonic stirring are evenly mixed.Prepared mixed liquor is painted the thickness of 100 μ m on glass plate.Be coated with rete 40 ℃ dry about 2 hours down, be in 50 ℃ the vacuum desiccator dry about 6 hours in temperature then.The porous electrolyte film that makes like this is at EC/DMC 1M LiPF 6Soaked about 10 minutes in the solution.After liquid electrolyte was adsorbed fully, the variation of weight was determined.Variation by weight records Δ AbValue is 7.5.By using AC impedence method can measure ionic conductivity is 2.0 * 10 -3S/cm.
Embodiment 4 (comparing embodiment)
2 gram paragonites and 0.26 gram PVdF are loaded in 20 milliliters of vials, mix 5 minutes with magnetic stirrer under dry state.In resulting mixture, add 4 milliliters of N-methyl pyrrolidones, continue then to stir and dissolve fully up to adhesive.In order to prevent to lump between the adhesive particle, when stirring, resulting solution is carried out 30 minutes ultrasonic agitation.Prepared mixed liquor is painted the thickness of 100 μ m on glass plate.Be coated with rete 40 ℃ dry about 2 hours down, in vacuum desiccator dry about 6 hours then, the temperature of vacuum desiccator was controlled at about 50 ℃.The difference of present embodiment and embodiment 1-3 is not have in this method pore structure to form step.The dielectric film that makes like this soaked in electrolyte about 10 minutes.After liquid electrolyte was adsorbed fully, the variation of weight was determined.Can measure conductivity by using AC impedence method.At room temperature recording ionic conductivity is 7.0 * 10 -4S/cm.
Embodiment 5
In order to measure porous solid electrolyte electrochemical stability, use stainless steel (#304) as work electrode, the lithium metal is as comparative electrode, and normal electrode is carried out the linear sweep voltammetry measurement.Employed electrochemical potentials is from 5.5 volts open circuit voltage in the linear sweep voltammetry.The sweep speed of linear sweep voltammetry is 10mV/ second.The electrolytical linear sweep voltammetry measurement result of porous solid by embodiment 1-(f), 1-(j), 1-(1) and 2-(s) preparation is shown A, B, C and the D among Fig. 2 respectively.
Embodiment 6
In order to measure the performance of the battery that uses solid electrolyte, oxide coated cathode, carbon anode and solid electrolyte according to the present invention are assembled into the finished product battery, then the finished product battery are charged and discharge test.The finished product battery is a laminate form, carries out the lamination preparation by target, anode and dielectric film, and liquid electrolyte is adsorbed by dielectric film.Use the direct current of the speed (C/2 speed) of reversible capacitance charging in 2 hours to be 4.2V up to cell voltage, the direct current of 4.2V reuses then, reduces to C/10mA up to electric current.Next, use discharging current, its velocity of discharge is reduced to 2.5V or 2.75V (C/2 speed) for discharge voltage within 2 hours.Charging and discharge test are repeated to carry out, and discharge capacity is along with the variation of charging and discharge is measured.Battery constitutes and test result is summarised in the table 3 also as shown in Figure 3.In table 3, the situation when solid electrolyte refers to that liquid electrolyte is adsorbed by dielectric film.In addition, the solid electrolyte among the embodiment 4 does not carry out battery testing.
Table 3
Embodiment Negative electrode Anode Solid electrolyte Figure
Active material Electric conducting material Adhesive Additive Active material Electric conducting material Adhesive Additive
v LiCoO 2 Carbon black PVdF Paragonite Graphite Carbon black PVdF Paragonite Ex.1-(e) Fig. 3-E
w LiCoO 2 Carbon black PVdF Zeolite Graphite Carbon black PVdF Zeolite Ex.1-(j) Fig. 3-F
x LiCoO 2 Carbon black PVdF Zeolite Graphite Carbon black PVdF Zeolite Ex.1-(n) Fig. 3-G
y LiCoO 2 Carbon black P(VdF-HFP) Zeolite Graphite Carbon black P(VdF-HFP) Zeolite Ex.3 Fig. 3-H
z LiMn 2O 4 Carbon black P(VdF-HFP) Paragonite Graphite Carbon black P(VdF-HFP) Paragonite Ex.2-(q) Fig. 3-I
Fig. 3 has shown the variation with respect to initial discharge capacity in recharge and the discharge process of battery by each embodiment preparation.(solid adsorbent ratio z) contains organic adsorbent such as polymer for embodiment 6-v, w, and the solid electrolyte of (embodiment 6-x) has shown better battery performance can to confirm use to contain inorganic adsorbent from test result.In addition, going back susceptible of proof uses the solid adsorbent of the wet method preparation according to the present invention to show better battery performance than the solid adsorbent by dry process (embodiment 6-y).That is to say, contain inorganic adsorbent and generally battery performance (charging and discharge performance etc.) has been played better influence, though the not significant difference of the character of dielectric film or solid electrolyte (ionic conductivity, mechanical strength etc.) itself by the solid electrolyte that wet method prepares.
Industrial applicibility
Feature according to micropore solid electrolyte of the present invention is as follows:
They have high mechanical properties, and this makes their suitable for making become film;
They have higher ionic conductivity with respect to liquid electrolyte, and this is to be suitable for adsorbing liquid electrolyte owing to introduce the adsorbent of polymeric matrix, and the transmission of lithium ion is not produced restriction;
Do not resemble usually gel-type polymer electrolyte, because lithium salts runs into traces of moisture and will decompose. Be not imported into thereby they are without any need for especially except the moisture atmosphere in the process of preparation dielectric film;
Because adsorbent wherein has electrochemical stability, they have the electrochemical potentials working range (electrochemical potential window) of wide region; And
Because electrolyte preparation method simply makes them be easy to automatic batch production.
In addition, owing to have good associativity and import after the liquid electrolyte variation of volume little between negative electrode and anode, micropore solid electrolyte according to the present invention can reduce the skin resistance between electrolyte and the electrode. Thereby, according to the suitable electrolyte as charged lithium cells of micropore solid electrolyte of the present invention. The solid electrolyte that contains inorganic adsorbent has shown good mechanical strength stability, heat endurance and electrochemical stability with respect to the solid electrolyte that contains organic adsorbent, thereby the minimizing of discharge capacity is few in the process of recharge and discharge. When importing loose structure in electrolyte, wet method is more effective and more stable than dry method. When using the micropore solid electrolyte to make electrochemical cell, many micropores solid electrolyte has shown excellent service behaviour, such as top carry to the minimizing of discharge capacity few.

Claims (7)

1. be used for the solid electrolyte of rechargeable battery, comprise:
Thickness is 10-200 μ m and the dielectric film with microcellular structure; And
Percentage by weight is the liquid electrolyte with ionic conductivity of 30-90%, and described weight is based on the electrolytical gross weight that comprises liquid electrolyte,
Wherein said dielectric film contains the adsorbent that particle size is no more than 40 μ m, and its content is 30-95% with respect to the gross weight of the dry state dielectric film that does not contain liquid electrolyte by weight, wherein
Described adsorbent is the mixture that is selected from a kind of particle in following group or two or more particles, and described group comprises that porous polymer particles, mineral grain, composite oxide particle, the aperture of being made by oxide or polymer material are particle and other commercially available adsorbents of the mesoporous molecular sieve of 2-30nm;
The liquid electrolyte of described ionic conductivity is dissolved in by the lithium salts with one or more in mixture of one or more organic solvents and obtains.
2. solid electrolyte according to claim 1, wherein said dielectric film prepares by wet method, may further comprise the steps:
The mixture of dissolving adsorbent and polymer adhesive in a kind of solvent that is applicable to polymer adhesive,
Make resulting solution be transformed into form membrane,
Exchange described solvent with a kind of non-solvent of polymer adhesive that is applicable to, and dry then resulting material
Wherein, described polymer adhesive is to be selected from following group one or more mixture, described group comprises: poly-inclined to one side 1, the 1-difluoroethylene, 1, the copolymer of 1-difluoroethylene and hexafluoropropylene, 1, the copolymer of 1-difluoroethylene and maleic anhydride, polyvinyl chloride, polymethyl methacrylate, polymethacrylates, cellulose triacetate, polyurethanes, polysulfones, polyethers, polyethylene, polypropylene, poly(ethylene oxide), polyisobutene, polybutadiene, polyvinyl alcohol, polyacrylonitrile, polyimides, polyvinyl formal, acrylonitrile butadiene rubber, ethylene-propylene-diene-monomer, four (ethene glycol), two propylene esters, dimethyl silicone polymer, Merlon and silicon polymer, or their copolymer;
The solvent of dissolve polymer adhesive is the mixture that is selected from following group one or both or multiple solvent composition, and described group comprises: N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, oxolane, acetonitrile, cyclohexanone, chloroform, carrene, hexamethyl phosphoramide, methyl-sulfoxide, acetone and dioxane; And
The non-solvent that is used for polymer adhesive is one or both or the multiple mixture of being made up of following substances, and described material is selected from: water, ethanol, ethylene glycol, glycerol, acetone, carrene, ethyl acetate, butanols, amylalcohol, hexanol and ether.
3. solid electrolyte according to claim 1, wherein said dielectric film may further comprise the steps by dry process:
The mixture of dissolving adsorbent and polymer adhesive in a kind of solvent that is applicable to polymer adhesive,
In resulting solution, add non-solvent, pore-forming agent and the impregnating agent that is applicable to polymer adhesive, and
Make resulting mixture form film, the resulting film of intensive drying then
Wherein, described polymer adhesive is to be selected from following group one or more mixture, described group comprises: poly-inclined to one side 1, the 1-difluoroethylene, 1, the copolymer of 1-difluoroethylene and hexafluoropropylene, 1, the copolymer of 1-difluoroethylene and maleic anhydride, polyvinyl chloride, polymethyl methacrylate, polymethacrylates, cellulose triacetate, polyurethanes, polysulfones, polyethers, polyethylene, polypropylene, poly(ethylene oxide), polyisobutene, polybutadiene, polyvinyl alcohol, polyacrylonitrile, polyimides, polyvinyl formal, acrylonitrile butadiene rubber, ethylene-propylene-diene-monomer, four (ethene glycol), two propylene esters, dimethyl silicone polymer, Merlon and silicon polymer, or their copolymer;
The solvent of dissolve polymer adhesive is the mixture that is selected from following group one or both or multiple solvent composition, and described group comprises: N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, oxolane, acetonitrile, cyclohexanone, chloroform, carrene, hexamethyl phosphoramide, methyl-sulfoxide, acetone and dioxane; And
The non-solvent that is used for polymer adhesive is one or both or the multiple mixture of being made up of following substances, and described material is selected from: water, ethanol, ethylene glycol, glycerol, acetone, carrene, ethyl acetate, butanols, amylalcohol, hexanol and ether.
4. one kind according to claim 2 or 3 described solid electrolytes, wherein
Described solid electrolyte prepares by activation process, and described activation process is that the liquid electrolyte with ionic conductivity absorbs in the described dielectric film.
5. one kind according to the described solid electrolyte that is used for rechargeable battery of claim 1, wherein
Described porous polymer particles is the above mixture of one or both materials that is selected from polyethylene, polypropylene, polystyrene and polyurethanes, paper pulp, cellulose, cork and wood chip;
Described mineral grain is the mixture that is selected from one or more materials of clay, paragonite, montmorillonite and mica;
Described composite oxide particle is the mixture that is selected from one or more materials of zeolite, porous silica and Woelm Alumina;
Described lithium salts is for being selected from LiClO 4, LiBF 4, LiPF 6, LiAsF 6, LiSCN, LiCF 3SO 3, LiN (CF 3SO 2) 2, LiC (CF 3SO 2) 3One or more material;
Described organic solvent is for being selected from ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid Methylethyl ester, gamma-butyrolacton, 1,3-dioxane, oxolane, 2-methyltetrahydrofuran, methyl-sulfoxide, sulfolane, N, the mixture dimethyl ether of one or more materials of dinethylformamide, diethylene glycol dimethyl ether, triglyme and tetraethylene glycol
Lithium salt in described organic solvent is 0.5M-2M.
6. solid electrolyte that is used for rechargeable battery according to claim 1, wherein said adsorbent are one or both or the multiple mixture of being made up of following substances, and described material is selected from mineral grain, composite oxide particle and mesoporous molecular sieve.
7. chargeable lithium cell is made by following step:
The mixture of dissolving adsorbent and polymer adhesive in a kind of solvent that is applicable to polymer adhesive,
Make resulting solution change film forming,
Exchange described solvent with a kind of non-solvent of polymer adhesive that is applicable to, dry resulting material forms the many micropores dielectric film that contains adsorbent,
With negative electrode and anode the be assembled together formation battery of prepared dielectric film with preparation respectively, and then
The liquid electrolyte that makes resulting battery absorption have ionic conductivity
Wherein, described adsorbent is the mixture that is selected from a kind of particle in following group or two or more particles, and described group comprises that porous polymer particles, mineral grain, composite oxide particle, the aperture of being made by oxide or polymer material are particle and other commercially available adsorbents of the mesoporous molecular sieve of 2-30nm;
The liquid electrolyte of described ionic conductivity is dissolved in by the lithium salts with one or more in mixture of one or more organic solvents and obtains;
Described polymer adhesive is to be selected from following group one or more mixture, described group comprises: poly-inclined to one side 1, the 1-difluoroethylene, 1, the copolymer of 1-difluoroethylene and hexafluoropropylene, 1, the copolymer of 1-difluoroethylene and maleic anhydride, polyvinyl chloride, polymethyl methacrylate, polymethacrylates, cellulose triacetate, polyurethanes, polysulfones, polyethers, polyethylene, polypropylene, poly(ethylene oxide), polyisobutene, polybutadiene, polyvinyl alcohol, polyacrylonitrile, polyimides, polyvinyl formal, acrylonitrile butadiene rubber, ethylene-propylene-diene-monomer, four (ethene glycol), two propylene esters, dimethyl silicone polymer, Merlon and silicon polymer, or their copolymer;
The solvent of dissolve polymer adhesive is the mixture that is selected from following group one or both or multiple solvent composition, and described group comprises: N-methyl pyrrolidone, dimethyl formamide, dimethylacetylamide, oxolane, acetonitrile, cyclohexanone, chloroform, carrene, hexamethyl phosphoramide, methyl-sulfoxide, acetone and dioxane; And
The non-solvent that is used for polymer adhesive is one or both or the multiple mixture of being made up of following substances, and described material is selected from: water, ethanol, ethylene glycol, glycerol, acetone, carrene, ethyl acetate, butanols, amylalcohol, hexanol and ether.
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