CN107591511A - Composite film material for lithium battery and its preparation method and application - Google Patents
Composite film material for lithium battery and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of composite film material for lithium battery, wherein, the composite film material includes polymer film and coated in the conductive particles layer on the side surface of polymer film one, wherein the one or more in the particle of the conductive particles layer containing ionic conductor material, the particle of ion-electron mixed conductor material and the particle of electron conductor material.Present invention also offers the preparation method of composite film material and the application in chargeable lithium metal battery.In addition, the invention provides the liquid metal lithium battery comprising above-mentioned composite film material and solid metallic lithium battery.
Description
Technical field
The invention belongs to electrochemistry and novel energy resource material technology field, and in particular to a kind of compound film material for lithium battery
Material and its preparation method and application.
Technical background
In recent years, fast-developing electric automobile and energy storage industry to lithium ion battery energy density, cost, cyclicity and
Security proposes higher requirement.
Lithium anode is considered as forth generation negative pole, has and reaches as high as 3860mAh/g capacity and relatively low deposition
Current potential (- 3.04V).300wh/kg can be brought up to by battery energy density by doing negative pole using lithium metal, can effectively be alleviated electronic
The mileage anxiety of automobile, while can also use without lithium positive pole, reduce battery cost.
Lithium metal is the unlimited expansion of negative electrode volume as the key problem of negative pole.In addition, lithium metal as negative pole also
Problems be present：Lithium deposition is uneven in charging process, and local substantial amounts of lithium deposition can accelerate volumetric expansion, solid so as to cause
Body dielectric substrate (SEI) ruptures；Li dendrite is formed, dendrite penetrates readily through short circuit caused by barrier film；Dendrite has higher chemistry anti-
The activity answered, easily reacted with electrolyte, consume electrolyte；And the dissolving abjection of dendrite root lithium, easily it is broken dendrite,
Dead lithium is formed, causes battery storehouse energy efficiency low.
The conventional method of protection metal is including the use of oxide, sulfide solid electrolyte, polymer solids electricity at present
Xie Zhi, liquid film for additive, and the methods of modification reduces effective current density and volumetric expansion is carried out to lithium metal structure.
Although the use of solid electrolyte has prevented the side reaction of lithium anode and solution but oxide electrolysis plasma membrane is easy
It is broken, it is not easy to make the battery of high power capacity.Especially, although the potsherd of micron thickness can stop lithium dendrite growth, can not improve
Battery energy density.
Sulfide electrolyte has higher electrical conductivity and flexibility, by be cold-pressed can prepare preferably it is compound just
Pole, but positive pole and sulfide electrolyte are difficult to be well mixed, and the preparation condition of sulfide electrolyte is high, air stability
Difference.
Although copolymer solid electrolyte has certain flexibility, can suppress lithium dendrite growth, but its electrical conductivity is relatively low, battery
Internal resistance is larger.
Although film for additive can effectively improve the storehouse energy efficiency of battery, suppress lithium dendrite growth, when addition
When agent exhausts, lithium deposition is uneven, and SEI can still rupture, and dendrite may proceed to grow.And electrolyte can be consumed always, in battery
Resistance dramatically increases, the change that polarizes is big, capacity attenuation.
In lithium ion battery, the United States Patent (USP) US6 of the bulletin on the 13rd of August in 2002,432,586B1 and 2006 year January 12
Day U.S. Patent Application Publication US2006/0008700A1 discloses a kind of coating inorganic layer (such as aluminum oxide, titanium dioxide
Silicon, calcium carbonate, titanium dioxide etc.) the ceramic diaphragm based on porous substrate, can effectively prevent inside lithium ion cell dendrite
Internal short-circuit caused by growth, improve the security performance of lithium ion battery.
For lithium metal battery, dendritic growth phenomenon is more serious., can not be effective only with ceramic coating membrane technology
Ground prevents dendritic growth.
In consideration of it, it is necessary to propose the membrane material that a kind of security is good, ionic conductivity is high, is easy to scale preparation.
The content of the invention
Therefore, in view of the above-mentioned problems, the invention provides a kind of composite film material for lithium battery and preparation method thereof
And application.
The purpose of the present invention is achieved through the following technical solutions.
In a first aspect, the invention provides a kind of composite film material for lithium battery, wherein, the composite film material bag
Containing polymer film and coated in the conductive particles layer on the side surface of polymer film one, wherein the conductive particles layer contain from
Particle, the particle of ion-electron mixing conductor material and one kind or more in the particle of electron conductor material of sub- conductor material
Kind.
According to composite film material provided by the invention, wherein, the ionic conductor material is selected from Li4-rGe1-rPrS4、
Li7P3S11、Li3PS4、Li1+xAlxGe2-x(PO4)3、Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、
Li7-nLa3Zr2-nTanO12、Li7-nLa3Zr2-nNbnO12、Li7-2nLa3Zr2-nWnO12、Li7-2nLa3Zr2-nTenO12、Li7- 3nGenLa3Zr2O12And Li7-3nAlnLa3Zr2O12In one or more, wherein, 0≤r≤1,0≤x≤2,0≤y≤2/3,0
≤ z≤2,0≤m≤2,0≤n≤0.6.
In some specific embodiments, the ionic conductor material is selected from Li1.5Al0.5Ge1.5(PO4)3、
Li7P3S11、Li3PS4、Li0.5La0.5TiO3、LiZr0.5Ti1.5(PO4)3、Li1.4Al0.4Ti1.6(PO4)3And Li3.5Ge0.5P0.5S4In
One or more.
As used herein, term " ion-electron mixing conductor material " refers between ionic conductor material and electricity
A kind of solid material between sub- conductor material, it has ionic conductivity and electron conduction concurrently simultaneously.
In some embodiments, the ion-electron mixing conductor material is selected from native graphite, Delanium, soft
Carbon, hard carbon, silicon, germanium, lithium titanate, titanium dioxide, cupric oxide, zinc oxide, iron oxide, manganese oxide, tin oxide, stannous oxide, oxygen
Change the one or more in sub- silicon, iron sulfide and ferrous sulfide.
According to composite film material provided by the invention, wherein, the electron conductor material is selected from carbon black, Ke Qin carbon
(KB), acetylene black, Super P, graphene, single wall or multi-walled carbon nanotube, copper powder, aluminium powder, ruthenic oxide and molybdenum dioxide
In one or more.
According to composite film material provided by the invention, wherein, the particle of the conductive particles layer containing ionic conductor material
With the particle of electron conductor material.
In some embodiments, the ionic conductor material can account for the ionic conductor material and the electronic conductor
The 50-99.5wt% of total amount of material, preferably 50-99wt%.Similarly, in some embodiments, the electronic conductor material
Material can account for the ionic conductor material and the 0.5-50wt% of the electron conductor material total amount, preferably 1-50wt%.
In the present invention, particle, the particle of the ion-electron mixing conductor material for the ionic conductor material
And/or the average grain diameter of the particle of the electron conductor material does not have particular/special requirement.However, in some embodiments, it is described
The particle of the particle of ionic conductor material, the particle of the ion-electron mixing conductor material and/or the electron conductor material
Average grain diameter be preferably 10-1000nm, more preferably 10-500nm.
For example, in some embodiments, the average grain diameter of the particle of the electron conductor material or a diameter of 10-
1000nm；And in some embodiments, electron conductor material can be graininess, threadiness, tubulose or sheet.
According to composite film material provided by the invention, wherein, the thickness of the conductive particles layer is 0.2-10 μm, is preferably
0.1-2μm。
According to composite film material provided by the invention, wherein, the gross thickness of the composite film material is 1-100 μm, preferably
For 5-20 μm.
According to composite film material provided by the invention, wherein, the polymer film is porose monofilm or multilayer film, with
And the material of each tunic of the monofilm or the multilayer film can be each independently polyethylene (PE), polypropylene (PP),
Kynoar (PVDF), Kynoar-hexafluoropropene (PVDF-HFP), polyimides (PI), makrolon (PC), poly- pair
PET, polybutylene terephthalate (PBT), polyethers acetone, poly or cellulose
(cellulose)。
According to composite film material provided by the invention, wherein, the gross thickness of the monofilm or multilayer film is 0.1-50 μm,
Porosity is 5-80%.In some embodiments, the thickness of each tunic is each independently 0.1-30 μm in the multilayer film.
In some embodiments, the polymer film is free from the polymer dielectric film in hole, the polymer electrolytic
Plasma membrane includes polymeric substrate and conductive lithium salts.Term " not apertures " used herein generally refer to porosity 1% with
Under material.
In some specific embodiments, the polymeric substrate is selected from PEO (PEO), PPOX
(PPO), makrolon (PC), Kynoar (PVDF), polymethyl methacrylate (PMMA), polyacrylonitrile, perfluorinated sulfonic acid
One or more in film (Nafion) and sulfonated polyether-ether-ketone (SPEEK).
In some specific embodiments, the conductive lithium salts is selected from lithium hexafluoro phosphate, LiBF4, perchloric acid
Lithium, trifluoromethyl sulfonic acid lithium, double (trimethyl fluoride sulfonyl sub-) amine lithiums, double fluorine sulfimide lithiums and di-oxalate lithium borate one kind or
It is a variety of.
In some embodiments, the conductive lithium salts accounts for the 1-10wt% of the polymer dielectric film.
According to composite film material provided by the invention, wherein, another side surface of the polymer film is coated with side of the positive electrode
Applicator, the side of the positive electrode applicator select the one or more of following material：
The particle of (1) second ionic conductor material, it can be with the particle phase of the ionic conductor material in conductive particles layer
It is same or different, and for selected from Li4-rGe1-rPrS4、Li7P3S11、Li3PS4、Li1+xAlxGe2-x(PO4)3、Li3yLa2/3-yTiO3、
LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、Li7-2n-jAnLa3Zr2-jBjO12And Li7-2n-2jAnLa3Zr2-jCjO12In one
Kind is a variety of, wherein, 0≤r≤1,0≤x≤2,0≤y≤2/3,0≤z≤2,0≤m≤2,0≤n≤3,0≤j≤2, A Ge
And/or Al, B are Nb and/or Ta, C are Te and/or W.
In some embodiments, the average grain diameter of the particle of second ionic conductor material is 10-500nm.
In some embodiments, the thickness of the second coated ionic conductor material is 0.2-10 μm, preferably 0.5-2
μm。
(2) in aluminum oxide, magnesia, zinc oxide, titanium oxide, lithium titanate, lithium phosphate, lithium fluoride and LiFePO4
One or more particles, its average grain diameter are 10-500nm, and the thickness of the side of the positive electrode applicator of coating is 0.2-10 μm, is preferably
0.5-2μm。
(3) polymer-modified layer, selected from Kynoar-hexafluoropropene decorative layer, Kynoar decorative layer, poly- carbon
Acid esters decorative layer, PEO decorative layer, PPOX decorative layer or dimethyl silicone polymer decorative layer, the polymer
The thickness of decorative layer is 0.2-10 μm, preferably 0.2-2 μm.
According to composite film material provided by the invention, the conductive particles layer and/or the side of the positive electrode applicator are each only
On the spot include binding agent.
In some embodiments, described adhesive is selected from carboxymethyl cellulose, Kynoar, polymethylacrylic acid
One or more in methyl esters, pectin, polyamide, polyimides, Lithium polyacrylate (PAALI).
In some embodiments, described adhesive accounts for the conductive particles layer and/or the side of the positive electrode independently of one another
The 0.5-20wt% of applicator, preferably 0.5-5wt%.
Second aspect, the invention provides a kind of preparation method of the composite film material, wherein, methods described include with
Lower step：
(1) by of the particle of ionic conductor material, the particle of ion-electron mixing conductor material and electron conductor material
One or more in grain are mixed with solvent and optionally adhesive to form slurry；
Preferably, the solvent is selected from 1-METHYLPYRROLIDONE, acetonitrile, acetone, DMF, water and second
One or more in alcohol etc.；
Preferably, the dosage of the solvent is 80-98wt%.
(2) by the side surface of slurry prepared by step (1) coated in polymer film, solvent is removed, is led so as to be formed
Body stratum granulosum.
According to method provided by the invention, wherein, methods described is further comprising the steps of (3)：In the polymer film
Side of the positive electrode applicator is coated on another side surface.
In the present invention, side of the positive electrode applicator can also be coated by the way that slurry is made.Preparing side of the positive electrode applicator
When, adhesive can be similarly used, and it can be identical or different with the adhesive used in step (1), does not have here
There is particular determination.
According to method provided by the invention, wherein, described adhesive is selected from carboxymethyl cellulose, Kynoar, gathered
One or more in methyl methacrylate, pectin, polyamide, polyimides and Lithium polyacrylate (PAALI).
According to method provided by the invention, wherein, described adhesive accounts for the conductive particles layer and/or institute independently of one another
State the 0.5-20wt% of side of the positive electrode applicator, preferably 0.5-5wt%.
In addition, what the preparation of slurry was known to those skilled in the art, and any of technology can be passed through
Come carry out.For example, slurry can be formed by physical mixed.
The third aspect, the invention provides application of the composite film material in chargeable lithium metal battery.
According to the present invention some embodiments, the invention provides a kind of chargeable lithium metal battery, wherein, it is described can
Charging lithium metal battery includes negative pole, the composite film material, positive pole and liquid electrolyte, wherein, the conductive particles aspect
To negative pole.
In some embodiments, positive pole include LiFePO4, lithium manganese phosphate, lithium ferric manganese phosphate, cobalt acid lithium, lithium nickelate,
One or more positive poles containing lithium in LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, lithium-rich oxide or nickel ion doped
Material；And in other embodiments, positive pole includes manganese oxide, vanadium oxide, chromium oxide, iron oxide, manganous fluoride, fluorination
Iron, ferric phosphate, manganese phosphate, fluorographite, graphite oxide, ferric sulfate, Ni, Mn oxide, iron cobalt manganese composite oxide, iron sulfide,
One or more in manganese sulfide, cobalt sulfide, nickel sulfide, titanium sulfide, sulphur, sulphur carbon, lithium sulfide and oxyvanadium compound.
In some embodiments, the positive pole can also include bonding agent, conductive additive or solid electrolyte etc..
In some embodiments, the negative pole includes the work that lithium metal, lithium alloy or the compound containing lithium metal are formed
Property film.
In some specific embodiments, the lithium alloy include containing aluminium, magnesium, boron, silicon, tin lithium alloy.
In some specific embodiments, the example of the compound containing lithium metal include lithium metal and carbon, silicon, aluminium,
The physical mixture and copper nitride, lithium copper nitrogen, lithium iron nitrogen, lithium manganese nitrogen, lithium cobalt nitrogen and Li that copper, tin are formed7MP3(wherein, M=
Ti, V or Mn).
In some specific embodiments, lithium anode film thickness is 2-100 μm.The lithium anode film can be with
Directly use, or be compressed on the paper tinsel, net, porous membrane of conduction, the conductive paper tinsel, net, the material of porous membrane include
Carbon, copper, titanium, stainless steel, nickel etc..
In some embodiments, the chargeable lithium metal battery also comprising can during charging and discharging lithium battery it is complete
Portion or the liquid electrolyte for being partially converted into solid electrolyte, wherein, the liquid electrolyte include lithium salts, organic solvent and into
Film additive.
In some specific embodiments, the lithium salts is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, six
Fluorine arsenic acid lithium, trifluoromethyl sulfonic acid lithium, double (trimethyl fluoride sulfonyl sub-) amine lithiums, double fluorine sulfimide lithiums, di-oxalate lithium borate and
The one or more of lithium perchlorate.
In some specific embodiments, the concentration of lithium salts is 0.1-1mol/L in the liquid electrolyte.
In some specific embodiments, the organic solvent be selected from methyl ethyl carbonate (EMC), γ-penta lactones (γ-
VL), γ-fourth lactones (γ-BL), dimethyl carbonate (DMC), propene carbonate (PC), diethyl carbonate (DEC), ethylene carbonate
Ester (EC), glycol dimethyl ether (DME), (two, three, four) glycol dimethyl ether, 1,3- dioxolanes (DOL), tetrahydrofuran
(THF), the one or more in dimethyl sulfoxide (DMSO) (DMSO) and acetonitrile (AN).
In some specific embodiments, the film for additive is selected from ethylene sulfite (ES), sulfurous acid propylene
Ester (PS), vinylene carbonate (VC), dimethyl sulfite (DMS), diethyl sulfite (DES), 1,2- trifluoroacetic acids
Base ethane (BTE), ethylene carbonate vinylene (VEC), fluorinated ethylene carbonate (FEC), cyclohexyl benzene (CHB), succinonitrile
(SN), adiponitrile (AND), 1,3- propane sultones (1,3-PS), fluoromethyl carbonic ester (FMC), diphenyl disulfide, connection
One or more in benzene, anthracene and phenanthrene.
In some embodiments, the liquid electrolyte can also include boundary moisture agent such as fluoro-ether, fire-retardant addition
Agent such as phosphate, and ionic liquid etc..
According to embodiment of the present invention, the invention provides a kind of liquid metal lithium battery, the liquid metal lithium electricity
Pond is melted into by the chargeable lithium metal battery discharge and recharge and is made.
According to embodiment of the present invention, the invention provides a kind of solid metallic lithium battery, the solid metal lithium electricity
Pond is melted into by the chargeable lithium metal battery discharge and recharge and is made.
The liquid metal lithium battery and the solid metallic lithium battery contain above-mentioned solid electrolyte film.
In some embodiments, the liquid metal lithium battery or solid metallic lithium battery can be by including following steps
It is prepared by rapid method：
(1) lithium metal battery is assembled, wherein, barrier film of the composite film material as lithium battery, and the conductor
Granulosa is towards negative pole；With
(2) discharge and recharge chemical conversion is carried out to the lithium metal battery of assembling.
In some embodiments, discharge and recharge chemical conversion can be in a manner of multi-stage constant current or constant voltage in heating and true
Carried out under empty condition.
It is not intended to bound by theory, it is believed that, after the completion of battery assembling, heated in a manner of multi-stage constant current or constant voltage
With progress discharge and recharge chemical conversion under vacuum condition, the liquid electrolyte for being advantageous to add in chargeable lithium metal battery is in lithium metal
The interface side and the particle in conductive particles layer of the composite film material towards metal lithium electrode side of electrode and composite film material
The current potential on surface is reduced when being less than electrolyte electrochemical window, the particle of the ionic conductor material in conductive particles layer, from
Gap in-situ preparation solid electrolyte (SEI) layer of the particle of son-electron mixed conductor material or the particle of electron conductor material,
SEI can be filled in the gap in composite film material, and porous barrier film is converted into dense solid electrolyte membrane.The cause formed
Close layer can prevent liquid electrolyte contacting metal lithium, can dendrite inhibition growth, while the distribution of lithium ion can be regulated and controled to allow lithium
Deposition is more uniform, and conductive particles layer also has a higher electrical conductivity with SEI composite diaphragms in itself, and battery polarization is relatively low.
In some embodiments, the porosity of the film after chemical conversion is less than 10%, it might even be possible to reaches less than 4%.
In some embodiments, in discharge and recharge formation process, the current density of constant current operation is 0.01-10C, constant pressure
Operation can be divided into 1-3 voltage section, and temperature can be at 20 DEG C -150 DEG C, and vacuum can be controlled in normal pressure~1Pa.
After the completion of battery assembling, it can heat and filled under vacuum condition in a manner of multi-stage constant current or constant voltage
Electric discharge chemical conversion, after the completion of liquid electrolyte is converted into solid electrolyte, can further add such as carbonates, ethers
Liquid electrolyte, it is further carried out second of discharge and recharge chemical conversion.
Compared with prior art, the present invention at least has advantages below：
(1) composite film material for lithium battery can be melted into in-situ preparation solid electrolyte film, operation by discharge and recharge
Simply, can compatible existing battery manufacturing process, reduce further the production cost of solid metal lithium battery；
(2) growth and suppression of Li dendrite can effectively be suppressed provided by the present invention for the composite film material of lithium battery
Puncture of the Li dendrite processed to barrier film, reduces and is further chemically reacted between lithium metal and electrolyte, can effectively protect gold
Belong to lithium electrode, reduce the efflorescence of lithium, improve lithium battery security.
Brief description of the drawings
Hereinafter, embodiment of the present invention is described in detail with reference to accompanying drawing, wherein：
Fig. 1 be charge and discharge cycles before the composite film material surface of the embodiment of the present application 1 scanning electron microscopic picture (SEM)；
Fig. 2 be charge and discharge cycles before the composite film material section of the embodiment of the present application 1 scanning electron microscopic picture (SEM)；
Fig. 3 is the solid of generation after circulating 100 weeks in the lithium ion battery containing the composite film material of the embodiment of the present application 1
The scanning electron microscopic picture (SEM) of dielectric film；
Fig. 4 is the solid of generation after circulating 100 weeks in the lithium ion battery containing the composite film material of the embodiment of the present application 1
The scanning electron microscopic picture (SEM) of dielectric film section；
Fig. 5 is the charge and discharge of 50,100,150,200 weeks before the lithium metal battery containing the composite film material of the embodiment of the present application 1
Electric curve map；
Fig. 6 is after lithium metal battery containing the composite film material of comparative example 1 circulates 100 weeks, towards negative side coating it is non-from
The scanning electron microscopic picture (SEM) on the Ranvier's membrane surface of subconductivity particle；
Fig. 7 is after lithium metal battery containing the composite film material of comparative example 1 circulates 100 weeks, towards negative side coating it is non-from
The scanning electron microscopic picture (SEM) of the Ranvier's membrane section of subconductivity particle.
Embodiment
The present invention is further described in detail with reference to embodiment, the embodiment provided is only for explaining
The bright present invention, the scope being not intended to be limiting of the invention.
In the following embodiments, used material is as follows：
The polymeric film material of table 1
| Polymer film is numbered | Composition |
| Polymer film 1 | Polypropylene (PP) |
| Polymer film 2 | Polyethylene (PE) |
| Polymer film 3 | Kynoar (PVDF) |
| Polymer film 4 | Kynoar-hexafluoropropene (PVDF-HFP) |
| Polymer film 5 | Polyimides |
| Polymer film 6 | PEI |
| Polymer film 7 | Makrolon |
| Polymer film 8 | Poly- aramid fiber |
| Polymer film 9 | Cellulose |
| Polymer film 10 | PEO (PEO) |
| Polymer film 11 | Polybutylene terephthalate (PBT) |
| Polymer film 12 | Polyethers acetone |
| Polymer film 13 | Polyacrylonitrile |
| Polymer film 14 | Perfluoro sulfonic acid membrane (Nafion) |
| Polymer film 15 | Sulfonated polyether-ether-ketone (SPEEK) |
Particle employed in conductive particles layer of the table 2 towards negative side
The side of the positive electrode applicator of table 3
Conductive lithium salts in the polymer film of table 4
| Conductive lithium salts numbering | Composition |
| Lithium salts 1 | Lithium hexafluoro phosphate (LiPF6) |
| Lithium salts 2 | Double (trimethyl fluoride sulfonyl is sub-) amine lithium (LiN (CF3SO2)2) |
| Lithium salts 3 | LiBF4 (LiBF4) |
| Lithium salts 4 | Lithium perchlorate (LiClO4) |
| Lithium salts 5 | Trifluoromethyl sulfonic acid lithium LiCF3SO3) |
| Lithium salts 6 | Li(CF3SO2)3) |
| Lithium salts 7 | Hexafluoroarsenate lithium (LiAsF6) |
| Lithium salts 8 | Di-oxalate lithium borate (LiBOB) |
Organic solvent in the liquid electrolyte of table 5.1
| The numbering of organic solvent | Composition |
| Solvent 1 | Methyl ethyl carbonate (EMC) |
| Solvent 2 | Dimethyl carbonate (DMC) |
| Solvent 3 | Dimethyl carbonate (DMC) |
| Solvent 4 | Carbonic acid (two) ethyl ester (DEC) |
| Solvent 5 | Ethylene carbonate (EC) |
| Solvent 6 | Glycol dimethyl ether (DME):1,3- dioxolanes (DOL)=1:1 (volume ratio) |
| Solvent 7 | Propene carbonate (PC) |
| Solvent 8 | Tetrahydrofuran (THF) |
| Solvent 9 | Dimethyl carbonate (DMC)：Ethylene carbonate (EC)=1:1 (volume ratio) |
| Solvent 10 | Dimethyl carbonate (DEC)：Ethylene carbonate (EC)=1:1 (volume ratio) |
Film for additive in the liquid electrolyte of table 5.2
The positive electrode of table 6
| The numbering of positive electrode | Composition |
| Positive electrode 1 | Cobalt acid lithium |
| Positive electrode 2 | LiFePO4 |
| Positive electrode 3 | LiMn2O4 |
| Positive electrode 4 | Nickle cobalt lithium manganate |
| Positive electrode 5 | Nickel cobalt lithium aluminate |
| Positive electrode 6 | Lithium-rich oxide |
| Positive electrode 7 | Nickel ion doped |
| Positive electrode 8 | MnO2 |
| Positive electrode 9 | FeS2 |
| Positive electrode 10 | FeF3 |
| Positive electrode 11 | S |
| Positive electrode 12 | Ferric phosphate |
| Positive electrode 13 | O2 |
| Positive electrode 14 | Ferrosilite |
The preparation of composite film material：
(1) by the particle of ion-electron mixing conductor material, the particle of electron conductor material, ionic conductor material
One or more in grain are mixed with adhesive and solvent to form slurry；
The solvent be selected from 1-METHYLPYRROLIDONE, acetonitrile, acetone, DMF, water and ethanol, it is described
The mass fraction that solvent accounts for the slurry is 80%-98%, wherein, with each negative side ceramic conductor particle to the bonding used
Agent, solvent and its dosage are shown in Table 7.
(2) by a side surface of the slurry coated in polymer film prepared in step (1), dry to remove solvent, from
And form conductive particles layer；With
(3) slurry of side of the positive electrode applicator is coated on another side surface of above-mentioned polymer film, dries and removes solvent, its
In, with each side of the positive electrode applicator to being shown in Table 8 with the adhesive, solvent and its dosage that use.
Table 7
Table 8
In the examples below, Ranvier's membrane used (composite film material) by polymer film, coated in polymer film towards
The particle of the conductive particles layer of negative side, ion conductor particle or ionic conductivity coated in polymer film towards side of the positive electrode
Grain is formed.The species of polymer film, thickness, porosity, the particle type of the conductive particles layer coated towards negative side, particle chi
Very little, coating layer thickness, the coating species towards side of the positive electrode, particle size, the overall porosity of coating layer thickness and Ranvier's membrane are shown in Table
9。
Table 9
Embodiment 1
Embodiment 1 provides one kind can charge and discharge lithium metal battery and solid metallic lithium battery prepared therefrom.Specifically,
(1) chargeable lithium metal battery is assembled, wherein, barrier film of the composite film material as lithium battery, and the conductor
Particle level is to negative pole；With
(2) discharge and recharge chemical conversion is carried out to the lithium metal battery of assembling.
The assembling of simulated battery is carried out in the glove box containing argon gas, and composite film material numbering is the basis in table 9
Film 1, just extremely cobalt acid lithium electrode, are lithium metal to electrode, lithium salts LiPF6, lithium salt 1mol/L, organic solvent is
EC：DMC=1:1 (that is, solvent 9).
Constant current charge-discharge pattern test, charge cutoff voltage 4.2V are carried out using discharge and recharge instrument, discharge cut-off voltage is
3.0V, test and carried out under 10C current density, test temperature is 25 DEG C.Battery is torn open in argon gas glove box after 100 weeks
Open, the solid electrolyte film and metal lithium electrode surface topography to generation are observed.
Fig. 1 shows the scanning electron microscopic picture (SEM) on the composite film material surface of embodiment 1 before charge and discharge cycles.Fig. 3 shows
Show after circulating 100 weeks in the lithium ion battery containing the composite film material of embodiment 1, the scanning electricity of the solid electrolyte film of generation
Mirror picture (SEM).Ranvier's membrane surface in situ, which is can be seen that, from Fig. 1 and Fig. 3 generates solid electrolyte film, solid electrolyte film
The growth in situ on the particle of conductive particles layer, and conductive particles layer is covered.
Fig. 2 shows the scanning electron microscopic picture (SEM) of the composite film material section of embodiment 1 before charge and discharge cycles.Fig. 4 shows
Show after circulating 100 weeks in the lithium ion battery containing the composite film material of embodiment 1, the solid electrolyte film section of generation is swept
Retouch electron microscopic picture (SEM).From Fig. 2 and Fig. 4 profile scanning electron microscope (SEM) as can be seen that conductive particles layer particle
Gap growth in situ solid electrolyte film.
Result above shows, during charging and discharging lithium battery, in lithium metal battery negative pole side, liquid electrolyte passes through
Electrochemical reaction, the solid electrolyte material with ion conductivity is gradually converted on Ranvier's membrane, and then produces solid
Dielectric film.
Fig. 5, which is shown before the solid metallic lithium battery containing the composite film material of embodiment 1 50,100,150,200 weeks, to be filled
Discharge curve.From Fig. 5 it can be found that battery has high coulombic efficiency and excellent cycle performance.
Embodiment 2-31
The embodiment of the present application 2-31 is provided can charge and discharge lithium metal battery and solid metallic lithium battery prepared therefrom.Tool
Body,
(1) chargeable lithium metal battery is assembled, wherein, barrier film of the composite film material as lithium battery, and the conductor
Particle level is to negative pole；With
(2) discharge and recharge chemical conversion is carried out to the lithium metal battery of assembling.
Being assemblied in the glove box containing argon gas for simulated battery is carried out, and composite film material numbering corresponds to the base in table 9
Plinth film 2-31, it is lithium metal to electrode, used lithium salts, solvent, additive and positive electrode are as shown in table 10, wherein,
Lithium salt is 1mol/L, additive concentration 2wt%.Meanwhile table 10 gives the operating temperature and discharge and recharge electricity of battery
Press scope.
Table 10
Before charge and discharge cycles and circulated 100 weeks by the composite film material of film 2-31 based on SEM observation numberings
Surface and the SEM figures of section, its display base film 2-31 surface in situ afterwards generates solid electrolyte film, solid electrolyte
Film growth in situ on the particle of conductive particles layer, and conductive particles layer is covered, and between the particle of conductive particles layer
Gap growth in situ solid electrolyte film.
Embodiment 32-46
32-46 of the embodiment of the present invention is provided can charge and discharge lithium metal battery and solid metallic lithium battery prepared therefrom.
Specifically,
(1) chargeable lithium metal battery is assembled, wherein, barrier film of the composite film material as lithium battery, and the conductor
Particle level is to negative pole；With
(2) discharge and recharge chemical conversion is carried out to the lithium metal battery of assembling.
Being assemblied in the glove box containing argon gas for simulated battery is carried out, and composite film material numbering is the Ranvier's membrane in table 9
32-46, is lithium metal to electrode, lithium salts LiPF6, lithium salt 1mol/L, organic solvent EC：DMC=1:1 is (that is, molten
Agent 9).
Constant current charge-discharge pattern test, charge cutoff voltage 4.2V are carried out using discharge and recharge instrument, discharge cut-off voltage is
3.0V, test and carried out under 10C current density, test temperature is 25 DEG C.
Surface and section of the composite film material before charge and discharge cycles and after circulation 100 weeks are observed by SEM
SEM schemes, and its display base film surface in situ generates solid electrolyte film, and solid electrolyte film is on the particle of conductive particles layer
Growth in situ, and conductive particles layer is covered, and the gap growth in situ solid electrolyte of the particle in conductive particles layer
Film.
Result above shows, during charging and discharging lithium battery, in lithium metal battery negative pole side, liquid electrolyte passes through
Electrochemical reaction, gradually gradated on Ranvier's membrane as the solid electrolyte material with ion and/or electronic conduction ability,
And then produce solid electrolyte film.
Comparative example 1
Comparative example 1 is used for illustrating when Ranvier's membrane coats on the surface towards negative side coated with ionic conductivity particle
During layer, it is impossible to in-situ preparation solid electrolyte.
Wherein, the polymer film of comparative example 1 is polypropylene (PP) film, and the thickness of PP films is 20um, porosity 10%-
20%, ionic conductivity particle (aluminum oxide, particle size 10um) is coated towards the side of negative pole in Ranvier's membrane, its thickness is
5um。
The assembly simulation battery in the glove box containing argon gas, wherein, just extremely cobalt acid lithium electrode is metal to electrode
Lithium, electrolyte contain 1mol/L LiPF6, 2wt% additives 2 and solvent 9.
Constant current charge-discharge pattern test, charge cutoff voltage 4.2V are carried out using discharge and recharge instrument, discharge cut-off voltage is
3.0V, test and carried out under 10C current density, test temperature is 60 DEG C.After circulating 100 weeks by battery in argon gas glove box
Take apart, composite film material, and metal lithium electrode surface topography are observed.
After Fig. 6 shows that the lithium metal battery containing the composite film material of comparative example 1 circulates 100 weeks, coated towards negative side
The scanning electron microscopic picture (SEM) on the Ranvier's membrane surface of ionic conductivity particle.Do not have as shown in fig. 6, pressing close to negative side in Ranvier's membrane
There is in-situ preparation solid electrolyte film.
After Fig. 7 shows that the lithium metal battery containing the composite film material of comparative example 1 circulates 100 weeks, coated towards negative side
The scanning electron microscopic picture (SEM) of the Ranvier's membrane section of ionic conductivity particle.As shown in fig. 7, in ionic conductivity material oxidation
Without generation solid electrolyte film between alumina particles.
Embodiment described above, the purpose of the present invention, technical scheme and beneficial effect are carried out further specifically
It is bright, it should be understood that and the foregoing is only embodiments of the invention, the protection domain being not intended to limit the present invention,
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., it should be included in the present invention's
Within protection domain.
Claims (12)
1. a kind of composite film material for lithium battery, wherein, the composite film material includes polymer film and coated in described
Conductive particles layer on the side surface of polymer film one, wherein the particle of the conductive particles layer containing ionic conductor material, ion-
One or more in the particle of electron mixed conductor material and the particle of electron conductor material.
2. composite film material according to claim 1, wherein, the ion-electron mixing conductor material is selected from natural
Graphite, Delanium, soft carbon, hard carbon, silicon, germanium, lithium titanate, titanium dioxide, cupric oxide, zinc oxide, iron oxide, manganese oxide, oxygen
Change the one or more in tin, stannous oxide, the sub- silicon of oxidation, iron sulfide and ferrous sulfide；
Preferably, the ionic conductor material is selected from Li4-rGe1-rPrS4、Li7P3S11、Li3PS4、Li1+xAlxGe2-x(PO4)3、
Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、Li7-nLa3Zr2-nTanO12、Li7-nLa3Zr2- nNbnO12、Li7-2nLa3Zr2-nWnO12、Li7-2nLa3Zr2-nTenO12、Li7-3nGenLa3Zr2O12And Li7-3nAlnLa3Zr2O12In
One or more, wherein, 0≤r≤1,0≤x≤2,0≤y≤2/3,0≤z≤2,0≤m≤2,0≤n≤0.6；It is highly preferred that
The ionic conductor material is selected from Li1.5Al0.5Ge1.5(PO4)3、Li7P3S11、Li3PS4、Li0.5La0.5TiO3、LiZr0.5Ti1.5
(PO4)3、Li1.4Al0.4Ti1.6(PO4)3And Li3.5Ge0.5P0.5S4In one or more；
Preferably, the electron conductor material is selected from carbon black, Ke Qin carbon, acetylene black, Super P, graphene, single wall or more
One or more in wall carbon nano tube, copper powder, aluminium powder, ruthenic oxide and molybdenum dioxide.
3. composite film material according to claim 1 or 2, wherein, the conductive particles layer contains ionic conductor material
The particle of particle and electron conductor material；
Preferably, the ionic conductor material accounts for the ionic conductor material and the 50- of the electron conductor material total amount
99.5wt%, preferably 50-99wt%；
Preferably, the electron conductor material accounts for the ionic conductor material and the 0.5- of the electron conductor material total amount
50wt%, preferably 1-50wt%.
4. composite film material according to any one of claim 1 to 3, wherein, the particle of the ionic conductor material, institute
The average grain diameter for stating the particle of ion-electron mixing conductor material and/or the particle of the mixed conductor material is 10-
1000nm, preferably 10-500nm；
Preferably, the thickness of the conductive particles layer is 0.2-10 μm, preferably 0.1-2 μm；
Preferably, the gross thickness of the composite film material is 1-100 μm, preferably 5-20 μm.
5. composite film material according to any one of claim 1 to 4, wherein, the polymer film is porose individual layer
Film or multilayer film, and each tunic of the monofilm or the multilayer film include polyethylene, polypropylene, gathered partially independently of one another
PVF, Kynoar-hexafluoropropene, polyimides, makrolon, polyethylene terephthalate, poly- terephthaldehyde
Sour butanediol ester, polyethers acetone, poly or cellulose；Preferably, the monofilm or multilayer film
Gross thickness is 0.1-50 μm, porosity 5-80%；It is highly preferred that the thickness of each tunic is each independently in the multilayer film
0.1-30μm；Or
The polymer film is free from the polymer dielectric film in hole, and the polymer dielectric film includes polymeric substrate and led
Electricity lithium salts, wherein, the polymeric substrate be selected from PEO, PPOX, makrolon, Kynoar,
One or more in polymethyl methacrylate, polyacrylonitrile, perfluoro sulfonic acid membrane and sulfonated polyether-ether-ketone；And wherein, institute
The lithium salts for stating conduction is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, trifluoromethyl sulfonic acid lithium, double (trifluoromethyl sulphurs
Acyl is sub-) one or more of amine lithium, double fluorine sulfimide lithiums and di-oxalate lithium borate；Preferably, the conductive lithium salts accounts for institute
State the 1-10wt% of polymer dielectric film.
6. composite film material according to any one of claim 1 to 5, wherein, another side surface of the polymer film
Coated with side of the positive electrode applicator, the side of the positive electrode applicator selects the one or more of following material：
The particle of (1) second ionic conductor material, selected from Li4-rGe1-rPrS4、Li7P3S11、Li3PS4、Li1+xAlxGe2-x(PO4)3、
Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、Li7-2n-jAnLa3Zr2-jBjO12And Li7-2n- 2jAnLa3Zr2-jCjO12In one or more, wherein, 0≤r≤1,0≤x≤2,0≤y≤2/3,0≤z≤2,0≤m≤2,0
≤ n≤3,0≤j≤2, A is Ge and/or Al, B are Nb and/or Ta, C are Te and/or W；
Preferably, the average grain diameter of the particle of second ionic conductor material is 10-500nm；
Preferably, the thickness of the second coated ionic conductor material is 0.2-10 μm, preferably 0.5-2 μm；
(2) one kind in aluminum oxide, magnesia, zinc oxide, titanium oxide, lithium titanate, lithium phosphate, lithium fluoride and LiFePO4
Or a variety of particles, its average grain diameter are 10-500nm, the thickness of the side of the positive electrode applicator of coating is 0.2-10 μm, preferably 0.5-
2μm；With
(3) polymer-modified layer, repaiied selected from Kynoar-hexafluoropropene decorative layer, Kynoar decorative layer, makrolon
Adorn layer, PEO decorative layer, PPOX decorative layer or dimethyl silicone polymer decorative layer, the polymer-modified layer
Thickness be 0.2-10 μm, preferably 0.2-2 μm.
7. composite film material according to any one of claim 1 to 6, wherein, the conductive particles layer and/or it is described just
Pole side applicator includes binding agent independently of one another；
Preferably, described adhesive is selected from carboxymethyl cellulose, Kynoar, polymethyl methacrylate, pectin, polyamides
One or more in amine, polyimides, Lithium polyacrylate；
Preferably, described adhesive accounts for the conductive particles layer and/or the 0.5- of the side of the positive electrode applicator independently of one another
20wt%, preferably 0.5-5wt%.
8. the preparation method of the composite film material any one of claim 1 to 7, wherein, methods described includes following step
Suddenly：
(1) particle of ionic conductor material, ion-electron is led in the particle of mixture material and the particle of electron conductor material
One or more mixed with solvent and optionally adhesive to form slurry；
Preferably, the solvent is in 1-METHYLPYRROLIDONE, acetonitrile, acetone, DMF, water and ethanol
One or more；
Preferably, the dosage of the solvent is 80-98wt%；
(2) by the side surface of slurry prepared by step (1) coated in polymer film, solvent is removed, so as to form conductor
Granulosa；
Preferably, described adhesive is selected from carboxymethyl cellulose, Kynoar, polymethyl methacrylate, pectin, polyamides
One or more in amine, polyimides and Lithium polyacrylate；
Preferably, described adhesive accounts for the 0.5-20wt% of the conductive particles layer, preferably 0.5-5wt%.
9. according to the method for claim 8, wherein, methods described is further comprising the steps of (3)：In the polymer film
Side of the positive electrode applicator is coated on another side surface；
Preferably, the side of the positive electrode applicator contains adhesive, and the dosage of adhesive is 0.5-20wt%, preferably 0.5-
5wt%.
10. application of the composite film material in chargeable lithium metal battery any one of claim 1 to 7.
11. a kind of chargeable lithium metal battery, wherein, the chargeable lithium metal battery is included in negative pole, claim 1 to 7
Composite film material and positive pole described in any one, wherein, the conductive particles aspect is to negative pole；
Preferably, the chargeable lithium metal battery is also included and can be completely or partially converted into during charging and discharging lithium battery
The liquid electrolyte of solid electrolyte, wherein, the liquid electrolyte includes lithium salts, organic solvent and film for additive；
It is highly preferred that the lithium salts is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, trifluoromethyl
Sulfonic Lithium, double (trimethyl fluoride sulfonyl sub-) amine lithiums, double fluorine sulfimide lithiums, one kind or more of di-oxalate lithium borate and lithium perchlorate
Kind；It is highly preferred that the concentration of lithium salts is 0.1-1mol/L in the liquid electrolyte；
It is highly preferred that the organic solvent is selected from methyl ethyl carbonate, γ-penta lactones, γ-fourth lactones, dimethyl carbonate, carbonic acid
Propylene, diethyl carbonate, ethylene carbonate, glycol dimethyl ether, (two, three, four) glycol dimethyl ether, 1,3- dioxies ring penta
One or more in alkane, tetrahydrofuran, dimethyl sulfoxide (DMSO) and acetonitrile；
It is highly preferred that the film for additive is selected from ethylene sulfite, propylene sulfite, vinylene carbonate, diformazan
Base sulfite, diethyl sulfite, 1,2- trifluoroacetic acid bases ethane, ethylene carbonate vinylene, fluorinated ethylene carbonate,
Cyclohexyl benzene, succinonitrile, adiponitrile, 1,3- propane sultones, fluoromethyl carbonic ester, diphenyl disulfide, biphenyl, anthracene and phenanthrene
In one or more.
12. a kind of liquid metal lithium battery or solid metallic lithium battery, the liquid metal lithium battery or the solid metallic lithium
Battery is made as the chargeable lithium metal battery discharge and recharge chemical conversion described in claim 11.
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