阅读说明：本技术 固态电池的制备方法及固态电池 (The preparation method and solid state battery of solid state battery ) 是由 张健 黄宁 徐斌 于 2019-07-11 设计创作，主要内容包括：本发明提供一种固态电池的制备方法,其包括以下步骤：提供正极片、负极片和复合电解质浆料；复合电解质层的形成,在所述正极片和/或负极片的一侧表面涂布所述复合电解质浆料形成至少一层复合电解质层,固化后得到复合正极片和/或复合负极片；采用叠片或卷绕工艺将所述复合正极片与所述负极片、或者所述复合负极片与所述正极片、或者所述复合正极片与所述复合负极片贴合在一起,使得所述复合电解质层夹设在极片之间；辊压或冷等静压,即得固态电池。同时,本发明还提供一种固态电池。相较于相关技术,本发明提供的固态电池的制备方法及固态电池有助于提升电化学性能,且易于产业化。(The present invention provides a kind of preparation method of solid state battery comprising following steps: providing positive plate, negative electrode tab and composite electrolyte slurry；The formation of composite electrolyte layer is coated with the composite electrolyte slurry in a side surface of the positive plate and/or negative electrode tab and forms at least one layer of composite electrolyte layer, anode composite piece and/or composite negative plate are obtained after solidification；The anode composite piece is fit together with the positive plate or the anode composite piece with the composite negative plate with the negative electrode tab or the composite negative plate using lamination or winding process, so that the composite electrolyte layer is folded between pole piece；Roll-in or isostatic cool pressing are to get solid state battery.Meanwhile the present invention also provides a kind of solid state batteries.Compared to the relevant technologies, the preparation method and solid state battery of solid state battery provided by the invention help to promote chemical property, and are easy to industrialization.)

1. a kind of preparation method of solid state battery, which is characterized in that itself the following steps are included:

Positive plate, negative electrode tab and composite electrolyte slurry are provided；

The formation of composite electrolyte layer is coated with the combined electrolysis chylema in a side surface of the positive plate and/or negative electrode tab Material forms at least one layer of composite electrolyte layer, and anode composite piece and/or composite negative plate are obtained after solidification；

Using lamination or winding process by the anode composite piece and the negative electrode tab or the composite negative plate and it is described just Pole piece or the anode composite piece fit together with the composite negative plate, so that the composite electrolyte layer is folded in Between pole piece；

Roll-in or isostatic cool pressing are to get solid state battery.

2. the preparation method of solid state battery according to claim 1, which is characterized in that by mass percentage, described multiple Close electrolyte slurry component include inorganic solid electrolyte 1%~99%, organolithium ionic conductive polymer 1%~90%, The solvent of lithium salts 1%~50%, binder 0.5%~30% and surplus.

3. the preparation method of solid state battery according to claim 2, which is characterized in that the inorganic solid electrolyte is phosphorus Sour germanium aluminium lithium, phosphoric acid germanium titanium lithium, lithium lanthanum zirconium tantalum oxygen, Li-La-Ti oxygen, lithium lanthanum zirconium oxygen, aluminium oxide, zirconium oxide, Li₂S-A、Li₂S-A- B、Li₂S-MeS₂-P₂S₅And Li₂S-MeS₂-P₂S₅- B is one or more, wherein A indicates P₂S₅、SiS₂、GeS₂、B₂S₃And Al₂S₄ One or more of, Me indicates that one of Si, Ge, Sn and Al or a variety of, B indicate one of Cl, Br and I or a variety of.

4. the preparation method of solid state battery according to claim 2, which is characterized in that organic lithium ion conducting polymerization Object includes one of polyethylene oxide, succinonitrile, polyacrylonitrile and polymethyl methacrylate or a variety of.

5. the preparation method of solid state battery according to claim 2, which is characterized in that the lithium salts is lithium perchlorate, four Lithium fluoroborate, lithium hexafluoro phosphate, double trifluoromethanesulfonimide lithiums and hexafluoro close one of arsenic acid lithium or a variety of.

6. the preparation method of solid state battery according to claim 2, which is characterized in that the binder is polyvinylidene fluoride One of alkene, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropene, polyacrylonitrile and polyisobutene are a variety of.

7. the preparation method of solid state battery according to claim 2, which is characterized in that the solvent is acetonitrile, N, N diformazan Base formamide, N, N dimethyl acetamide, n-methyl-2-pyrrolidone, acetone, butanone, ethyl alcohol, propyl alcohol, isopropanol, butanol, first Benzene, dimethylbenzene, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, methyl formate, chloroform, dimethyl carbonate With one of diethyl carbonate or a variety of.

8. the preparation method of solid state battery according to claim 1, which is characterized in that the number of plies of the composite electrolyte layer Be 1~30 layer, every layer with a thickness of 1~50 μm.

9. the preparation method of solid state battery according to claim 8, which is characterized in that composite electrolyte described in adjacent two layers The component of layer is identical, but the content of each component is different.

10. the preparation method of solid state battery according to claim 1, which is characterized in that form the composite electrolyte layer Coating method include soak coating, slope flow coating, item seam coating, blade coating, extrusion coated, transfer coated and printing be coated with One of or it is a variety of.

11. a kind of solid state battery, which is characterized in that the solid state battery uses the described in any item preparation sides claim 1-10 Method is made, and the solid state battery includes positive plate, negative electrode tab and is folded between the positive plate and the negative electrode tab at least One layer of composite electrolyte layer.

[technical field]

The present invention relates to solid state cell technology field more particularly to the preparation methods and solid state battery of a kind of solid state battery.

[background technique]

Since nineteen ninety Sony company announces that novel high-power rechargeable lithium ion battery exploitation is completed, and successfully in Since 1991 are commercialized, lithium ion battery is rapidly developed.The specific energy of first generation lithium ion battery is only 200Wh·L^-1And 80Whkg^-1, and its specific energy has reached 560 WhL now^-1And 210Whkg^-1, even higher. As the application range of lithium ion battery gradually extends, everybody proposes the security performance, service life, energy density of battery Higher requirement.But since the problems such as side reaction and electrolyte leakage occur at electrode interface for liquid electrolyte, causes Lithium ion battery is worried by people always using safe.And the solid state battery for using solid electrolyte to assemble can be effectively Security risk brought by liquid electrolyte is solved, solid electrolyte will not volatilize and nonflammable, thus improve lithium-ion electric The security performance in pond；And solid electrolyte can effectively prevent short circuit problem caused by lithium metal dendrite, so that with lithium metal It is possibly realized as battery cathode；In addition, solid electrolyte can work in wider temperature range, electrochemical window Mouth is wider, has widened the use of electrode material.

Core as solid-state serondary lithium battery forms, and composite multi-layer solid union electrolyte layer has macroion conductance Rate, high safety performance, high capacity, high mechanical strength, flexibility are good and have the characteristics such as industrialization amplification.It studies both at home and abroad Composite solid electrolyte more concentrates on serving as solid polyelectrolyte filler using inorganic solid electrolyte, prepares organic-nothing Machine composite solid electrolyte.Such as a kind of preparation of Organic-inorganic composite dielectric film disclosed in CN201810400093, pass through Inorganic solid electrolyte is added in organic polyelectrolyte as solid packing, improves the mechanical performance of composite electrolyte membrane And ionic conductivity.It is excessively thin composite electrolyte easily occur but since this Organic-inorganic composite electrolysis film thickness needs are thicker Film bad mechanical strength leads to battery short circuit by Li dendrite puncture.In addition, external more use magnetron sputtering or pulse laser Prepared by the mode of deposition, this process costs are high, and production efficiency is low, it is difficult to realize industrialization.These technologies can not be well Solve the problems, such as that composite solid electrolyte easily grows that Li dendrite, ionic conductivity be low and industrialization amplification.

Therefore, it is really necessary to provide a kind of improved solid state battery and preparation method thereof to solve the above problems.

[summary of the invention]

The present invention solves the technical problem of single layer composite solid electrolyte layers due to the growth of Li dendrite, to lead It causing solid state battery short circuit, can not carry out the technical issues of industrialization, the present invention provides a kind of solid state battery and preparation method thereof, It can be effectively improved the interfacial contact of electrode and electrolyte layer, reduce the interface impedance of electrode and solid-state electrolyte layer, promoted solid The chemical property of state battery, and multi-gradient coating solid electrolyte effectively reduces solid state battery short-circuit risks, safety Can be good, it is easy to industrialization.

In order to solve the above technical problem, the present invention provides a kind of preparation methods of solid state battery comprising following steps:

Positive plate, negative electrode tab and composite electrolyte slurry are provided；

The formation of composite electrolyte layer is coated with the combined electrolysis in a side surface of the positive plate and/or negative electrode tab Chylema material forms at least one layer of composite electrolyte layer, and anode composite piece and/or composite negative plate are obtained after solidification；

Using lamination or winding process by the anode composite piece and the negative electrode tab or the composite negative plate and institute It states positive plate or the anode composite piece fits together with the composite negative plate, so that the composite electrolyte layer presss from both sides It is located between pole piece；

Roll-in or isostatic cool pressing are to get solid state battery.

In a kind of preferred embodiment of the preparation method of solid state battery provided by the invention, by mass percentage, institute State composite electrolyte slurry component include inorganic solid electrolyte 1%~99%, organolithium ionic conductive polymer 1%~ 90%, the solvent of lithium salts 1%~50%, binder 0.5%~30% and surplus.

In a kind of preferred embodiment of the preparation method of solid state battery provided by the invention, the inorganic solid electrolyte For phosphoric acid germanium aluminium lithium, phosphoric acid germanium titanium lithium, lithium lanthanum zirconium tantalum oxygen, Li-La-Ti oxygen, lithium lanthanum zirconium oxygen, aluminium oxide, zirconium oxide, Li₂S-A、 Li₂S-A-B、Li₂S-MeS₂-P₂S₅And Li₂S-MeS₂-P₂S₅- B is one or more, wherein A indicates P₂S₅、SiS₂、GeS₂、B₂S₃ And Al₂S₄One or more of, Me indicates that one of Si, Ge, Sn and Al or a variety of, B indicate one of Cl, Br and I Or it is a variety of.

In a kind of preferred embodiment of the preparation method of solid state battery provided by the invention, organic lithium ion conducting Polymer includes one of polyethylene oxide, succinonitrile, polyacrylonitrile and polymethyl methacrylate or a variety of.

In a kind of preferred embodiment of the preparation method of solid state battery provided by the invention, the lithium salts is perchloric acid Lithium, LiBF4, lithium hexafluoro phosphate, double trifluoromethanesulfonimide lithiums and hexafluoro close one of arsenic acid lithium or a variety of.

In a kind of preferred embodiment of the preparation method of solid state battery provided by the invention, the binder is to gather inclined fluorine One of ethylene, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropene, polyacrylonitrile and polyisobutene are a variety of.

In a kind of preferred embodiment of the preparation method of solid state battery provided by the invention, the solvent is acetonitrile, N, N Dimethylformamide, N, N dimethyl acetamide, n-methyl-2-pyrrolidone, acetone, butanone, ethyl alcohol, propyl alcohol, isopropanol, fourth Alcohol, toluene, dimethylbenzene, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, methyl formate, chloroform, carbonic acid One of dimethyl ester and diethyl carbonate are a variety of.

In a kind of preferred embodiment of the preparation method of solid state battery provided by the invention, the composite electrolyte layer The number of plies be 1~30 layer, every layer with a thickness of 1~50 μm.

In a kind of preferred embodiment of the preparation method of solid state battery provided by the invention, compound electric described in adjacent two layers The component for solving matter layer is identical, but the content of each component is different.

In a kind of preferred embodiment of the preparation method of solid state battery provided by the invention, the composite electrolyte is formed The coating method of layer includes soak coating, slope flow coating, the coating of item seam, blade coating, extrusion coated, transfer coated and printing painting One of cloth is a variety of.

The present invention also provides a kind of solid state batteries, use the preparation method of the preparation method of solid state battery described above Be made, the solid state battery include positive plate, negative electrode tab and be folded between the positive plate and the negative electrode tab at least one Layer composite electrolyte layer.

Compared to the relevant technologies, the preparation method and solid state battery of solid state battery provided by the invention not only can effectively change The interfacial contact of kind electrode and electrolyte layer, reduces the interface impedance of pole piece and solid-state electrolyte layer, promotes the electricity of solid state battery Chemical property, and the mode of multi-gradient coating solid electrolyte, can effectively reduce solid state battery short-circuit risks, safety The good while of the invention preparation method of energy has the advantage amplified on a large scale.

[Detailed description of the invention]

To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other Attached drawing, in which:

Fig. 1 is the structural schematic diagram of solid state battery provided by the invention；

Fig. 2 is the flow diagram of the preparation method of solid state battery shown in Fig. 1；

Fig. 3 is the solid state battery first charge-discharge curve graph that the embodiment of the present invention 1 provides；

Fig. 4 is the solid state battery first charge-discharge curve graph that the embodiment of the present invention 3 provides；

Fig. 5 is the solid state battery first charge-discharge curve graph that the embodiment of the present invention 9 provides.

[specific embodiment]

Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that the described embodiments are merely a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts all other Embodiment shall fall within the protection scope of the present invention.

Referring to Fig. 1, being the structural schematic diagram of solid state battery provided by the invention.The solid state battery 100 includes anode Piece 1, negative electrode tab 2 and at least one layer of composite electrolyte layer 3 being folded between the positive plate 1 and the negative electrode tab 2.It is described just Anode of the pole piece 1 as the solid state battery 100, cathode of the negative electrode tab 2 as the solid state battery 100.

The positive plate 1 is made of positive electrode, uses known positive electrode, these positive electrodes include cobalt Sour lithium material, high pressure cobalt acid lithium material, high pressure cobalt phosphate lithium material, ternary nickel cobalt manganese material, LiFePO 4 material.

The negative electrode tab 2 is made of negative electrode material, uses known negative electrode material, these negative electrode materials include gold Belong to lithium material, silicon carbon material, lithium titanate material, lithium carbon material, graphite material.

The composite electrolyte layer 3 is formed in 2 surface of 1 surface of positive plate or the negative electrode tab by coating method, Or it is formed simultaneously in 2 surface of the positive plate 1 and the negative electrode tab.The composite electrolyte layer 3 is passed through into coating method shape 2 surface of positive plate 1 described in Cheng Yu and/or negative electrode tab can be effectively improved the interfacial contact of electrode and electrolyte layer, reduce electrode With the interface impedance of solid-state electrolyte layer, to promote the chemical property of solid state battery.

The composite electrolyte layer 3 can be set to multilayer, when forming composite electrolyte layer 3 described in multilayer, first in institute It states positive plate 1 and/or 2 surface of the negative electrode tab is coated with one layer of compound electrolyte material and is coated composite electrolyte after cured Material forms another layer composite electrolyte layer 3, that is, is coated after the upper one layer composite electrolyte layer 3 such as needing to solidify compound Electrolyte forms next layer composite electrolyte layer 3, is formed using this multi-gradient coating solid electrolyte compound Electrolyte layer can effectively reduce solid state battery short-circuit risks, have a safety feature, while to have extensive amplification etc. excellent for the technique Gesture.The number of plies of the composite electrolyte layer 3 is preferably 1~30 layer, every layer with a thickness of 1~50 μm.It is compound described in adjacent two layers The component of electrolyte layer 3 is identical, but the content of each component is different, in such a way that this multi-gradient is coated with solid electrolyte, Solid state battery short-circuit risks can be effectively reduced, are had a safety feature.

Further, the coating method for forming the composite electrolyte layer 3 includes soak coating, slope flow coating, item seam painting One of cloth, blade coating, extrusion coated, transfer coated and printing coating are a variety of.

Referring to Fig. 2, the present invention provides a kind of preparation method 200 of solid state battery, with solid-state shown in Fig. 1 of the present invention It is illustrated for battery, specifically includes the following steps:

Step S1 provides positive plate 1, negative electrode tab 2 and composite electrolyte slurry；

By mass percentage, the component of the composite electrolyte slurry include inorganic solid electrolyte 1%~99%, Organolithium ionic conductive polymer 1%~90%, lithium salts 1%~50%, binder 0.5%~30% and surplus solvent.

Wherein the inorganic solid electrolyte is phosphoric acid germanium aluminium lithium, phosphoric acid germanium titanium lithium, lithium lanthanum zirconium tantalum oxygen, Li-La-Ti oxygen, lithium Lanthanum zirconium oxygen, aluminium oxide, zirconium oxide, Li₂S-A、Li₂S-A-B、Li₂S-MeS₂-P₂S₅And Li₂S-MeS₂-P₂S₅- B is a kind of or more Kind, wherein A indicates P₂S₅、SiS₂、GeS₂、B₂S₃And Al₂S₄One or more of, Me indicates one of Si, Ge, Sn and Al Or it is a variety of, B indicates one of Cl, Br and I or a variety of.The organolithium ionic conductive polymer includes polyethylene oxide, amber One of amber nitrile, polyacrylonitrile, polymethyl methacrylate are a variety of.The lithium salts is lithium perchlorate, LiBF4, six Lithium fluophosphate, double trifluoromethanesulfonimide lithiums and hexafluoro close one of arsenic acid lithium or a variety of.The binder is to gather inclined fluorine One of ethylene, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropene, polyacrylonitrile and polyisobutene are a variety of.The solvent For acetonitrile, n,N dimethylformamide, N, N dimethyl acetamide, n-methyl-2-pyrrolidone, acetone, butanone, ethyl alcohol, third Alcohol, isopropanol, butanol, toluene, dimethylbenzene, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, ethyl acetate, formic acid first One of ester, chloroform, dimethyl carbonate and diethyl carbonate are a variety of.

It in this step, can be first respectively by inorganic solid electrolyte, organolithium when preparing the composite electrolyte slurry Ionic conductive polymer, lithium salts and binder, which are dissolved alone in solvent, forms mixture, then each mixture is mixed into one It rises and stirs evenly to form the composite electrolyte slurry, first can also be dissolved in shape in solvent together for two or three therein Resulting mixture, then admixed together stir evenly of each mixture is formed into the composite electrolyte slurry.

Step S2 is coated with the composite electrolyte slurry in a side surface of the positive plate 1 and/or negative electrode tab 2 and is formed At least one layer of composite electrolyte layer 3, obtains anode composite piece and/or composite negative plate after solidification；

In this step, can by being repeatedly coated with the composite electrolyte slurry, thus in the positive plate 1 and/or 2 surface of negative electrode tab forms composite electrolyte layer 3 described in multilayer.It is significant to note that when forming combined electrolysis described in multilayer When matter layer 3, it first is coated with one layer of composite electrolyte slurry in the positive plate 1 and/or 2 surface of the negative electrode tab, it is to be solidified Afterwards, it is coated the composite electrolyte slurry and forms another layer composite electrolyte layer 3, that is, upper one layer of compound electric such as need Solution matter layer 3 is coated composite electrolyte slurry after solidifying and forms next layer composite electrolyte layer 3, using this multi-gradient It is coated with solid electrolyte and forms composite electrolyte layer 3, solid state battery short-circuit risks can be effectively reduced, had a safety feature, simultaneously The technique has the advantages such as extensive amplification.The number of plies of the composite electrolyte layer 3 is preferably 1~30 layer, every layer with a thickness of 1 ~50 μm.The component of composite electrolyte layer 3 described in adjacent two layers is identical, but the content of each component is different, using this multilayer ladder The mode of degree coating solid electrolyte, can effectively reduce solid state battery short-circuit risks, have a safety feature.

Step S3, using lamination or winding process by the anode composite piece and the negative electrode tab 2 or the Compound Negative Pole piece fits together with the positive plate 1 or the anode composite piece with the composite negative plate, so that the compound electric Solution matter layer 3 is folded between pole piece；

Step S4, roll-in or isostatic cool pressing are to get solid state battery 100.

Embodiment 1-12 is described in further detail below in conjunction with attached drawing 2.