CN110165152A

CN110165152A - Solid-state anode composite material, preparation method and application

Info

Publication number: CN110165152A
Application number: CN201810139903.6A
Authority: CN
Inventors: 李静; 胡晨吉; 沈炎宾; 卢威; 吴晓东; 陈立桅
Original assignee: Suzhou Institute of Nano Tech and Nano Bionics of CAS
Current assignee: Suzhou Institute of Nano Tech and Nano Bionics of CAS
Priority date: 2018-02-11
Filing date: 2018-02-11
Publication date: 2019-08-23
Anticipated expiration: 2038-02-11
Also published as: CN110165152B

Abstract

The invention discloses a kind of solid-state anode composite material, preparation method and applications.The solid-state anode composite material includes: continuous organic phase, is assembled by the organic fibrous material at least with ion conductor function and is formed；Positive electrode active materials are distributed in hole contained by continuous organic phase；Electrolytic salt is distributed in inside organic fibrous material and in hole contained by the network structure that organic fibrous material and positive electrode active materials are constituted.The solid-state anode composite material is fexible film form.Solid-state anode composite material of the present invention has the features such as flexible, ionic conductivity is high, and electronic conductivity is high, processing performance, electrochemical performance.

Description

Solid-state anode composite material, preparation method and application

Technical field

The present invention relates to a kind of positive electrodes, and in particular to a kind of flexible solid anode composite material, flexible solid anode And preparation method thereof, and the application in electrochemical device, belong to electrochemical field.

Background technique

Past 20 years, along with the rapid development of portable consumer electronics industry, lithium ion battery due to energy density height, Cycle performance and high rate performance are good, and commercialization achieves immense success.However, the lithium-ion electric constantly occurred in the past few decades Pond safety accident is always the secret worry in field.

Lithium ion battery because occur internal temperature of battery caused by internal short-circuit or other reasons it is excessively high can occur it is on fire The hidden danger of explosion, it is most important the reason is that the organic electrolyte for having used high temperature inflammable is as lithium ion conducting network.So one Denier internal temperature of battery will cause battery because a variety of causes (such as internal short-circuit of battery) reaches the burning point of organic solvent It is on fire, or even explosion, battery energy density is higher, endangers bigger.This safety problem early in lithium ion battery be born at the beginning of just It has existed.Research closely for decades is thought, develops all-solid lithium-ion battery, it is possible to solve this safety from the root Hidden danger.

Specifically, due to no inflammable labile organic solvent, the security performance of battery is just in all-solid-state battery It is available to be substantially improved, while battery there will not be leakage, electrolyte dry-out, inflatable etc. influences asking for battery performance Topic.Moreover, the quality of all-solid-state battery is smaller, volume energy density is higher, and the design and assembly of battery are also more flexible.Therefore, Developing nonflammable all-solid lithium-ion battery is to develop high security, high-energy density, high power density, long circulation life Next battery eliminator inevitable choice.But restriction of the popularization and application of all-solid-state battery also by many technical aspects at present, All there are many skills in the exploitation of high conductivity solid electrolyte and the building of the positive cathode extremely electronic and ionic conductive network of inside Art challenge.

In general, the important necessary condition that battery can work is that the electronics and ion in system can be at one Quick conduction in continuous ion conductor network.For liquid state batteries, liquid can flow, and can continuously fill out It fills in inside battery, connects each electrode material granules, the transmission of ion is not a problem naturally.For industrialization at present For quasi- solid state battery, the electrolyte of gel state is also that can flow, and relatively good is filled in inside battery, connects each electricity The transmission of pole material granule, ion is not a problem yet.But for all-solid-state battery, the solid particle of inside battery it It is in close contact between even, is also usually the state for point-to-point contact, the ion transmission between particle is particularly difficult.

Current existing solid-state anode technology of preparing is usually to use inorganic ions conductor, conductive carbon and binder together with Then positive electrode active materials mixing paints pole piece, but constructs ion and electronic conduction network, electronic conduction with such method Performance does not have too big problem usually, but the contact between ion conductor and positive electrode is still point-to-point contact, interface resistance Resist it is larger, meanwhile, binder is contained in pole piece, tends to interfere with the transmission of lithium ion, thus ionic conduction network still have compared with Big problem.Therefore, the solid-state anode for developing high electronic and ionic conductivity is that one of realization all-solid-state battery industrialization is important Research direction.

Summary of the invention

The main purpose of the present invention is to provide a kind of solid-state anode composite materials, solid-state anode, to overcome the prior art In deficiency.

Another main purpose of the invention is to provide the preparation side of a kind of solid-state anode composite material and solid-state anode Method.

Another main purpose of the invention, which also resides in, provides the application of a kind of solid-state anode composite material and solid-state anode.

For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:

The embodiment of the invention provides a kind of solid-state anode composite material, it includes:

Continuous organic phase is assembled by the organic fibrous material at least with ion conductor function and is formed；

Positive electrode active materials are distributed in hole contained by continuous organic phase；

Electrolytic salt is distributed in the organic fibrous material inside and the organic fibrous material and positive electrode active materials In hole contained by the network structure of composition；

It can choose addition or the electronic conductor additive not added, Dispersed precipitate is in the solid-state anode composite material It is interior；And

It can choose addition or the inorganic ions conductor additive not added, Dispersed precipitate be compound in the solid-state anode In material；

Also, the solid-state anode composite material is flexible membrane form, and with a thickness of 30~500 μm.

In some preferred embodiments, the solid-state anode composite material includes:

Two dimension mainly formed by the organic fibrous material tight clusters, continuous or three-dimensional structure；

The positive electrode active materials being scattered in the two dimension or three-dimensional structure；And

The electrolysis being scattered in hole contained by the network structure that the organic fibrous material and positive electrode active materials are constituted Matter salt.

In some preferred embodiments, the organic fibrous material also has the function of electronic conductor.

Preferably, the solid-state anode composite material further includes Dispersed precipitate in the electricity in the solid-state anode composite material Sub- conductor additive.

Preferably, the solid-state anode composite material further includes Dispersed precipitate in the nothing in the solid-state anode composite material Machine ion conductor additive.

In embodiments of the present invention, continuous organic phase is formed by using aforementioned organic fibrous material, can use this A little organic fibers provide a large amount of special interface ion transfer passages, and the ionic conduction of solid-state anode composite material is substantially improved Rate.

The embodiment of the invention also provides a kind of solid-state anode composite material, it mainly by the pressurized processing of composite material, It is formed after being impregnated again with electrolyte salt solution；

The composite material includes:

Continuous organic phase, the continuous organic phase are that polymer solution is ejected into selected reception using electrostatic spinning technique Continuous two dimension or three-dimensional structure, the organic fibrous material are formed on face at least has the function of ion conductor；

While spraying the polymer solution, using electrostatic Spraying technique by the dispersion liquid of positive electrode active materials or The mixed dispersion liquid of positive electrode active materials and electronic conductor additive and/or inorganic ions conductor additive is ejected into described selected The network structure formed on receiving plane,

Wherein, the positive electrode active materials are distributed in hole contained by continuous organic phase, the electrolytic salt distribution The hole contained by the network structure that the organic fibrous material inside and the organic fibrous material and positive electrode active materials are constituted In hole；

Wherein, if the electronic conductor additive and/or inorganic ions conductor additive exist, the electronic conductor adds Add agent and/or inorganic ions conductor additive Dispersed precipitate in the solid-state anode composite material；

Wherein, the addition of positive electrode active materials can reinforce the dissociation of electrolytic salt, increase the free volume of organic phase, drop Low-crystallinity, while interacting with organic fibrous material, more interface ion transfer passages are formed, to further be promoted The ionic conductivity of solid-state anode composite material.

The embodiment of the invention also provides a kind of solid-state anode, including plus plate current-collecting body, covered on the plus plate current-collecting body There is solid-state anode composite material above-mentioned.

The embodiment of the invention also provides a kind of preparation methods of solid-state anode composite material comprising:

Polymer solution is ejected on selected receiving plane using electrostatic spinning technique and forms continuous two dimension or three-dimensional Structure, the organic fibrous material at least have the function of ion conductor；

While spraying the polymer solution, using electrostatic Spraying technique by the dispersion liquid of positive electrode active materials or The mixed dispersion liquid of positive electrode active materials and electronic conductor additive and/or inorganic ions conductor additive is ejected into described selected On receiving plane, obtained composite material progress pressurized treatments are made into its densification later, the positive electrode active materials is made to be distributed in company In hole contained by continuous organic phase, then with the electrolyte salt solution dipping composite material, enter electrolytic salt described multiple Contained by the network structure that organic fibrous material inside and the organic fibrous material and positive electrode active materials in condensation material are constituted Hole in, form the solid-state anode composite material；

In embodiments of the present invention, by pressurized treatments, organic fibrous material can be made to form fine and close continuous organic phase, Then electrolytic salt is added again, solid-state can further be substantially improved just while electrolytic salt usage ratio is greatly decreased The ionic conductivity of pole composite material.

The embodiment of the invention also provides a kind of preparation methods of solid-state anode comprising: it prepares as the method previously described Solid-state anode composite material, and the solid-state anode composite material is uniformly covered on plus plate current-collecting body, it is positive to obtain solid-state.

The embodiment of the invention also provides a kind of solid-state anode composite materials above-mentioned or solid-state anode in preparation electrochemistry Purposes in device.

Compared with the prior art, the advantages of the present invention are as follows:

1) solid-state anode composite material provided by the invention has ionic conductivity height, electrochemical performance, and mechanics The advantages that performance is high, and processing performance is good, has broad application prospects；

2) preparation process of solid-state anode composite material provided by the invention is simple, without containing included by traditional anode pole piece Binder and complicated coating processes, can be improved the specific discharge capacity and volume and capacity ratio of anode, anode can with cathode and Diaphragm integration system is standby, improves interface compatibility and stability between electrode electrolyte；It can prepare in batches simultaneously and using original Expect at low cost, mild condition, without expensive production equipment, yield is high, and controllable, and repeatability and stability are good, Yi Shixian It is prepared by extensive batch；

3) preparation method of solid-state anode composite material provided by the invention can be suitable for different battery systems, be Quan Gu The research and development of state battery provide a good thinking, are not only applicable to the preparation of anode thin film, are readily applicable to own Inorganic material film preparation, have pervasive meaning.

Detailed description of the invention

Fig. 1 is the scanning electron microscope (SEM) photograph of positive electrode in the prior art；

Fig. 2 is the preparation flow schematic diagram of solid-state anode thin film in an exemplary embodiments of the invention；

Fig. 3 is the battery structure schematic diagram of solid-state anode composite material preparation in an exemplary embodiments of the invention；

Fig. 4 is the scanning electron microscope (SEM) photograph of the flexible solid anode thin film prepared in the embodiment of the present invention 1；

Fig. 5 is the photomacrograph of the flexible solid anode thin film prepared in the embodiment of the present invention 1；

Fig. 6 is the scanning electron microscope (SEM) photograph of obtained flexible solid anode thin film after lithium salts is added dropwise in the embodiment of the present invention 1；

Fig. 7 is the electrochemistry cycle performance figure of the flexible solid anode thin film prepared in the embodiment of the present invention 1；

Fig. 8 is the scanning electron microscope (SEM) photograph of the flexible solid anode thin film prepared in the embodiment of the present invention 2；

Fig. 9 is first charge-discharge curve graph when the flexible solid anode thin film prepared in the embodiment of the present invention 2 is used as anode；

Figure 10 is the scanning electron microscope (SEM) photograph of the flexible solid anode thin film prepared in the embodiment of the present invention 3；

Figure 11 is the charging and discharging curve of the flexible solid anode thin film prepared in the embodiment of the present invention 3；

Figure 12 is the scanning electron microscope (SEM) photograph of the flexible solid anode thin film prepared in the embodiment of the present invention 4；

Figure 13 is the scanning electron microscope (SEM) photograph of the flexible solid anode thin film prepared in reference examples 2 of the present invention.

Specific embodiment

For many defects of the prior art, inventor is studied for a long period of time and is largely practiced, and proposes skill of the invention Art scheme as follows will be further explained the technical solution, its implementation process and principle etc..It is understood, however, that Within the scope of the present invention, above-mentioned each technical characteristic of the invention and each technical characteristic specifically described in (embodiment) below it Between can be combined with each other, to constitute new or preferred technical side's scheme.Due to space limitations, I will not repeat them here.

A kind of solid-state anode composite material that the one aspect of the embodiment of the present invention provides, it includes:

In some embodiments of the present invention, the organic fibrous material also has the function of electronic conductor.Correspondingly, The solid-state anode composite material can only include positive electrode active materials, organic fibrous material and electrolytic salt.

In other embodiments of the invention, although the organic fibrous material also has the function of electronic conductor, But the solid-state anode composite material also may also include electronic conductor additive and/or inorganic ions conductor additive etc., with into The performance of one step improvement solid-state anode composite material.These electronic conductor additives and/or inorganic ions conductor additive can be with Dispersed precipitate is in the solid-state anode composite material.

In some embodiments of the present invention, the organic fibrous material only has the function of ion conductor.Correspondingly, The solid-state anode composite material may include positive electrode active materials, electronic conductor additive, organic fibrous material and electrolyte Salt.These electronic conductor additives can be with Dispersed precipitate in the solid-state anode composite material.

In some embodiments of the present invention, the organic fibrous material only has the function of ion conductor, and described Solid-state anode composite material may include positive electrode active materials, electronic conductor additive, inorganic ions conductor additive, organic fibre Tie up material and electrolytic salt.These electronic conductor additives, inorganic ions conductor additive can be with Dispersed precipitates in the solid-state In anode composite material.

In some preferred embodiments, the solid-state anode composite material with a thickness of 30~500 μm, preferably 50~ 300 μm, especially preferably 150~250 μm.

Further, the ionic conductivity of the solid-state anode composite material is 1.0x10^-4~1.0x10^-2S/cm。

Further, solid-state anode composite material ionic conductivity at 25 DEG C is 1.0x10^-4~1.0x10^-2S/ cm。

Further, the density of the solid-state anode composite material is 1~5g/cm³。

Further, the bend resistance intensity of the solid-state anode composite material is 1~20MPa.

In some preferred embodiments, the matter of solid-state anode composite material the Inner electrolysis matter salt and organic fibrous material Amount is than being 1:2~1:10, preferably 1:3~1:6.

Further, in the solid-state anode composite material electrolytic salt content be 1~10wt%, preferably 1~ 5wt%.

Preferably, the electrolytic salt can be lithium salts, such as double trifluoromethanesulfonimide lithiums (LiTFSI), lithium perchlorate (LiClO4), one such or two or more combination such as hexafluoroarsenate lithium (LiAsF6), lithium hexafluoro phosphate (LiPF6), It can be the lithium salts of molecular weight polymers, such as the bis- trifluoromethanesulfonimide lithiums of succinonitrile-, but not limited to this.In addition, described Electrolytic salt is also possible to electrolytic salt used in all secondary metals batteries such as sodium salt, magnesium salts, aluminium salt.

In some embodiments, the diameter of organic fibrous material is 50nm~2 μm in the solid-state anode composite material, excellent It is selected as 100nm~1 μm, further preferably 150nm~800nm, especially preferably 300nm~600nm.

Further, in the solid-state anode composite material organic fibrous material content be 5~60wt%, preferably 10 ~20wt%.

In some embodiments, the material of the organic fibrous material includes polymer polymerizing object, at least has ion Conducting function.

Preferably, the polymer includes polyacrylonitrile (PAN), polyethylene oxide, polyvinylpyrrolidone (PVP), gathers Any one in ethylene glycol, polymethyl methacrylate (PMMA), Kynoar (PVDF) and polytetrafluoroethylene (PTFE) (PTFE) Or two or more combinations, but not limited to this.

It is furthermore preferred that the organic fibrous material include conducting polymer with lead the formation of ionomer blend graft and There is the polymer of ion and electronic conductor function simultaneously.

In some preferred embodiments, in the solid-state anode composite material content of positive electrode active materials be 30~ 95wt%, preferably 50~90wt%, further preferably 60~80wt%, especially preferably 70~80wt%.In the present invention In, in 70wt% or more, the solid-state anode composite material still is able to have fine the content of positive electrode active materials particle Flexibility.

In some embodiments, the partial size of the inorganic positive electrode active materials particle is 2nm~20 μm, preferably 5nm~1 μm, further preferably 10nm~1 μm, especially preferably 20nm~1 μm.

In some preferred embodiments, the material of the positive electrode active materials can be oxide anode material, vulcanization Any one or any one presoma in object positive electrode, polyanion positive electrode etc. is also possible to sodium ion electricity Pond positive electrode, anode of magnesium ion battery material, aluminium ion cell positive material etc. are all to can be adapted for secondary cell just Pole material and its presoma.

Preferably, the material of the positive electrode active materials includes LiFePO4, LiMn2O4, cobalt acid lithium, nickle cobalt lithium manganate (Li (NiCoMn)O₂), any one or two or more combinations in LiMn2O4 and nickel ion doped, but not limited to this.

In some embodiments, the content of electronic conductor additive is 0~50wt% in the solid-state anode composite material, Preferably 0~20wt%, further preferably 0~10wt%.

Further, the electronic conductor additive includes acetylene black, Super P conductive black, Ketjen black, carbon nanometer Pipe, carbon fiber, any one or two or more combinations in electrically conductive graphite, but not limited to this.

In some embodiments, in the solid-state anode composite material inorganic ions conductor additive content be 0~ 70wt%, preferably 0~40wt%, further preferably 0~20wt%.

Further, the inorganic ions conductor additive include lithium ion conductor additive, sodium ion conductor additive, Magnesium ion conductor additive or aluminium ion conductor additive, wherein the lithium ion conductor additive includes NASICON type lithium pottery Porcelain electrolyte, Ca-Ti ore type lithium ceramic electrolyte, carbuncle type lithium ceramic electrolyte, LISICON type lithium ceramic electrolyte, Li₃N Type lithium ceramic electrolyte, lithiumation BPO₄Lead lithium ceramic electrolyte and with Li₄SiO₄It is any one in the lithium ceramic electrolyte of parent Kind or two or more combinations, such as can be lithium lanthanum zirconium tantalum oxygen (LLZTO), but not limited to this.

The additive amount of positive electrode active materials can be greater than 70wt% in solid-state anode composite material of the invention, and addition can be with The dissociation for reinforcing electrolytic salt increases the free volume of organic phase, crystallinity is reduced, to extend the circulation longevity of lithium ion battery Life, improves the coulombic efficiency of battery.Meanwhile in the case where being added with positive electrode active materials, solid-state anode of the invention is compound Organic fibrous material, positive electrode active materials and electrolytic salt three mutually cooperate in material, can further promote solid-state anode The ionic conductivity of composite material shows good chemical property in secondary cell application.

Preferably, the solid-state anode composite material is flexible film form.

A kind of solid-state anode composite material that the one aspect of the embodiment of the present invention provides, it is mainly by composite material through adding Pressure processing, then formed after being impregnated with electrolyte salt solution；

The composite material includes:

Wherein, the positive electrode active materials are distributed in hole contained by the continuous organic phase, the electrolytic salt It is distributed in inside the organic fibrous material and contained by the network structure that the organic fibrous material and positive electrode active materials are constituted Hole in；

In some embodiments, the material of the organic fibrous material includes polymer, at least has ionic conduction function Energy.

Preferably, in the electrostatic spinning technique, the spacing of electrostatic spinning liquid outlet and the receiving plane is 5~30cm, Electrostatic potential is 5~50KV.

Preferably, in the electrostatic Spraying technique, the spacing of electrostatic spray liquid outlet and the receiving plane is 5~30cm, Electrostatic potential is 5~50KV.

In some embodiments, the injection of the injection direction of the electrostatic spinning liquid outlet and the electrostatic spray liquid outlet Direction is at the angle less than 90 ° more than or equal to 0.

Preferably, the polymer solution and the dispersion liquid of the positive electrode active materials or the flow of the mixed dispersion liquid Than for 100:1~1:100, preferably 1:10~1:50, especially preferably 1:5~1:7.The present invention can by control spinning and Spraying the two flow rate prepares the fexible films of different positive electrode contents.

Further, the pressure of the pressurized treatments be 100KPa~20MPa, the time be 1~60 minute, preferably 1~ 10 minutes, temperature was 25~60 DEG C.

Further, the time of the dipping is 1 minute~24 hours, preferably 5~10 minutes.

Preferably, the solid-state anode composite material is membranaceous, especially preferably flexible film-like.

Generally, the addition of organic fibrous material assigns positive electrode flexibility in solid-state anode composite material of the invention Feature, can accomplish that very thin (10-20 microns) also keep good integrality and processing performance.And inorganic material can be effective The energy storage devices such as inhibition lithium ion battery in the growth of Li dendrite etc. mentioned to extend the cycle life of such equipment The coulombic efficiency of high battery.

Solid-state anode composite material provided by the invention has following performance characteristic: 1) ionic conductance is high (reaches electrification Learn device application demand)；2) there is special mechanical property still can finish when being made into very thin film with retentivity Whole property, bending is not broken, and machinability is good；3) good chemical property is shown in secondary cell application.

Preferably, the plus plate current-collecting body includes any one of aluminium foil, utter misery aluminium foil, carbon felt, carbon paper, but is not limited to This.

Further, the solid-state anode composite material is uniformly covered in plus plate current-collecting body surface, and solid-state anode Composite material with a thickness of 30~500 μm, preferably 50~300 μm, further preferably 150~250 μm, the ion at 25 DEG C Conductivity is 1.0x10^-4~1.0x10^-2S/cm。

It please refers to shown in Fig. 2, a kind of solid-state anode composite material that the other side of the embodiment of the present invention also provides Preparation method comprising:

Polymer solution (being properly termed as solution 1) is ejected on selected receiving plane using electrostatic spinning technique and forms company Continuous two dimension or three-dimensional structure, the organic fibrous material at least have the function of ion conductor；

While spraying the polymer solution, using electrostatic Spraying technique by the dispersion liquid of positive electrode active materials or The mixed dispersion liquid of positive electrode active materials and electronic conductor additive and/or inorganic ions conductor additive (is properly termed as solution 2) it is ejected on the selected receiving plane, obtained composite material progress pressurized treatments is made into its densification later, make the anode Active material is distributed in hole contained by continuous organic phase, then impregnates the composite material with electrolyte salt solution, makes electricity Solve the organic fibrous material inside and the organic fibrous material and positive electrode active materials structure that matter salt enters in the composite material At network structure contained by hole, form the solid-state anode composite material；

In embodiment above-mentioned, organic fibrous material is set to form fine and close continuous organic phase by pressurized treatments, after And electrolytic salt is added, organic polymer can further be substantially improved while electrolytic salt usage ratio is greatly decreased The ionic conductivity of solid-state anode composite material.

Preferably, the solid-state anode composite material is membranaceous, preferably fexible film form.

As one of preferred embodiment, the preparation method includes: that will be used to spray the electrostatic of the polymer solution Spinning liquid outlet with for spraying the dispersion liquid of the positive electrode active materials or the electrostatic spray of the mixed dispersion liquid goes out liquid Mouth is arranged in parallel in the form of in harness.

As one of preferred embodiment, the preparation method includes: the injection direction for making the electrostatic spinning liquid outlet Injection direction with the electrostatic spray liquid outlet is at the angle less than 90 ° more than or equal to 0.

As one of preferred embodiment, the shape of the electrostatic spinning liquid outlet and/or electrostatic spray liquid outlet includes Round or slit shape, preferably slit shape, wherein slit-type has higher production capacity.It can be made using the liquid outlet of narrow slit structure The dispersion liquid of the polymer solution and the positive electrode active materials that are ejected on receiving plane or mixed dispersion liquid distribution are more Add uniformly.

As one of preferred embodiment, the dispersion liquid of the positive electrode active materials or the mixed dispersion liquid also include There is surfactant, to prevent positive electrode active materials from settling in dispersion liquid, and causes the blocking and spray of electrostatic spray liquid outlet It penetrates unevenly, to influence the uniformity and performance of solid-state anode thin film to be formed.

Preferably, the surfactant is in the dispersion liquid of the positive electrode active materials or the mixed dispersion liquid Content is 0.1~1wt%.

Preferably, the surfactant can be selected be cationic surfactant, anionic surfactant etc. from Subtype surfactant, nonionic surface active agent, amphoteric surfactant, compound surfactant and other surfaces are living Property agent etc., but not limited to this.

As one of preferred embodiment, the preparation method further include: in receiving plane and electrostatic spinning liquid outlet and/or Apply extra electric field between electrostatic spray liquid outlet, and under the DC Electric Field, will be described using electrostatic spinning technique Polymer solution is ejected on the receiving plane, and, using electrostatic Spraying technique by the dispersion liquid of the positive electrode active materials Or mixed dispersion liquid is ejected on the receiving plane.

In some embodiments, the receiving plane is the surface of reception device.

Preferably, the reception device includes in roller reception device, plane reception device and aqueous solution reception device Any one or two or more combinations, but not limited to this.

In some embodiments, the receiving plane also has negative electrical charge generating device.

Further, disperse by the dispersion liquid of the polymer solution and the positive electrode active materials or the mixing When liquid is sprayed to the receiving plane, along described between the electrostatic spinning liquid outlet and electrostatic spray liquid outlet and the receiving plane The axial relative movement of reception device.

Further, disperse by the dispersion liquid of the polymer solution and the positive electrode active materials or the mixing When liquid is sprayed to the receiving plane, along described between the electrostatic spinning liquid outlet and electrostatic spray liquid outlet and the receiving plane The length direction or width direction of receiving plane carry out reciprocal relative motion.

Further, the receiving plane is set with the electrostatic spinning liquid outlet and electrostatic spray liquid outlet in set angle It sets.

Further, the set angle includes 0~89.9 °.

In some embodiments, by the dispersion liquid of the polymer solution and the positive electrode active materials or described mixed Dispersion liquid is closed to when the injection of the cylinder surface of the roller reception device, the roller keeps rotation status.Keep above-mentioned work A film can be obtained after making state for a period of time, products therefrom can be peeled from roller easily.

Further, the revolving speed of the roller reception device is 300~1000rpm.

In some embodiments, by the dispersion liquid of the polymer solution and the positive electrode active materials or described mixed When conjunction dispersion liquid is sprayed to the receiving plane, the dispersion liquid or described mixed of the polymer solution and the positive electrode active materials The flow-rate ratio for closing dispersion liquid is 100:1~1:100, and preferably 1:10~1:50, especially preferably 1:5~1:7 can pass through control Spinning processed and spraying the two flow rate prepare the fexible films of different positive electrode contents.

Preferably, the spacing of the electrostatic spinning liquid outlet and electrostatic spray liquid outlet and the receiving plane is 5~30cm.

Preferably, the electrostatic potential that the electrostatic spinning technique and electrostatic Spraying technique use is 5~50KV.

As one of preferred embodiment, the preparation method includes: the pressure with 100KPa~20MPa, will be from reception The film that face is collected is placed on roller press and is rolled repeatedly.

As one of preferred embodiment, the preparation method further include: the solid-state is being infiltrated just with electrolyte salt solution Pole composite material, time are 1 minute~24 hours, preferably 5~10 minutes, are dried later.

Further, the electrolytic salt can be lithium salts, such as double trifluoromethanesulfonimide lithiums (LiTFSI), perchloric acid Lithium (LiClO₄), hexafluoroarsenate lithium (LiAsF₆), lithium hexafluoro phosphate (LiPF₆) etc. one such or two or more combination, It can be the lithium salts of molecular weight polymers, such as the bis- trifluoromethanesulfonimide lithiums of succinonitrile-, but not limited to this.In addition, described Electrolytic salt is also possible to electrolytic salt used in all secondary metals batteries such as sodium salt, magnesium salts, aluminium salt.

In some embodiments, the preparation method includes: to dissolve the polymer in the first solvent, obtains the polymerization Object solution.

Further, first solvent includes all alcohol-based liquids such as water, N-Methyl pyrrolidone, ethyl alcohol, N, N- bis- Methylformamide, dimethyl sulfoxide, any one or two or more combinations in dimethyl acetamide etc. can dissolve aforementioned Polymer all liq, but it is not limited to this.

In some embodiments, the preparation method includes: that positive electrode active materials are dispersed in the second solvent, is obtained Obtain the dispersion liquid of the positive electrode active materials；

Alternatively, positive electrode active materials and electronic conductor additive and/or inorganic ions conductor additive are dispersed in In second solvent, the mixed dispersion liquid is obtained.

In some preferred embodiments, the material of the inorganic positive electrode active materials particle can be oxide anode material Any one or any one presoma in material, sulfide positive electrode, polyanion positive electrode etc., is also possible to sodium Ion battery positive electrode, anode of magnesium ion battery material, aluminium ion cell positive material etc. are all to can be adapted for secondary electricity The positive electrode and its presoma in pond.

Further, the inorganic ions conductor additive include lithium ion conductor additive, sodium ion conductor additive, Magnesium ion conductor additive or aluminium ion conductor additive, wherein the lithium ion conductor additive includes NASICON type lithium pottery Porcelain electrolyte, Ca-Ti ore type lithium ceramic electrolyte, carbuncle type lithium ceramic electrolyte, LISICON type lithium ceramic electrolyte, Li₃N Type lithium ceramic electrolyte, lithiumation BPO₄Lead lithium ceramic electrolyte and with Li₄SiO₄It is any one in the lithium ceramic electrolyte of parent Kind or two or more combinations, but not limited to this.

Preferably, second solvent can be dispersion aforementioned positive electrode active material, electronic conductor additive and it is inorganic from All liquid of sub- conductor additive can be in other ketone liquid such as the alcohol-based liquids such as water, ethyl alcohol, isopropanol, acetone Any one or two or more combinations, but it is not limited to this.

By above-mentioned technical proposal, the preparation process of solid-state anode composite material of the invention is simple, can prepare in batches and Low using cost of material, mild condition, without expensive production equipment, yield is high, and controllable, and repeatability and stability are good, It can be suitable for different battery systems, provide a good thinking for the research and development of all-solid-state battery, be not only applicable to just The preparation of very thin films is readily applicable to the preparation of all inorganic material films, has pervasive meaning.

Further, since the fiber of spinning itself is that have good flex capability, therefore it is also ensured that with the method system Standby film out similarly has flexibility, and can prepare different anodes by control spinning and spraying the two flow rate The fexible film of active material content.For this system, it is easy to carry out using technique, the easily controlled characteristic of preparation process can To realize a kind of preparation of flexible solid anode thin film.

The other side of the embodiment of the present invention additionally provides a kind of preparation method of solid-state anode comprising: according to preceding The method preparation solid-state anode composite material stated, and the solid-state anode composite material is uniformly covered on plus plate current-collecting body, Obtain solid-state anode.

The other side of the embodiment of the present invention additionally provides a kind of solid-state anode composite material above-mentioned or solid-state anode In preparing the purposes in electrochemical device.

Preferably, the electrochemical device includes energy storage device and/or electrochromic device, and the energy storage device includes electricity Pond.

Further, the electrochromic device includes black and white e-book, color e-book etc..

For example, including comprising anode, cathode and electrolyte, the anode the embodiment of the invention also provides a kind of battery Solid-state anode composite material above-mentioned.

Further, the battery can be all-solid-state battery.

Further, using solid-state anode composite material above-mentioned or solid-state anode thin film as working electrode, and, with common Secondary cell electrolysis matter be electrolyte, with common secondary battery cathode material (metal, oxide, carbon material etc.) be to electricity Pole, the Symmetrical cells of sandwich structure consisting, as shown in Figure 3.According to the difference of selected metal electrode, the battery can be lithium Battery, sode cell, magnesium cell, aluminum cell etc., but not limited to this.

Below by way of several embodiments and in conjunction with the attached drawing technical solution that present invention be described in more detail.However, selected Embodiment be merely to illustrate the present invention, and do not limit the scope of the invention.

Embodiment 1

The commercially available Kynoar of about 1g (PVDF) powder is dissolved in the n,N-Dimethylformamide (DMF) of about 10g, Obtain Kynoar solution.About 1g is commercially available, granular size is about 700nm iron phosphate powder and 0.14g is commercially available Acetylene black is added in the ethyl alcohol that about 20g contains about 1wt% surfactant and is dispersed with stirring to obtain positive electrode active materials and second The mixed dispersion liquid of acetylene black.Spinning is carried out simultaneously under the high pressure of about 20KV with by spraying, two syringe needles are apart from roller reception device Distance be about 8cm, the flow velocity of Kynoar solution is about 10 μ l/min in spinning syringe needle, positive-active material in spraying syringe needle The flow velocity for expecting dispersion liquid is about 80 μ l/min, after so work about 8 hours, can take a flexibility off from roller reception device Anode thin film is then rolled at about 100KPa about 60 minutes, can be prepared by just very thin with a thickness of 80 μm of flexible solid Film, ionic conductivity 1.0x10^-2S/cm, density 2.5g/cm³, wherein the content of positive electrode active materials reaches about 70wt%.Scanning electron microscope (SEM) photograph by flexible solid anode thin film manufactured in the present embodiment is shown in Figure 4, photomacrograph referring to Shown in Fig. 5.In addition, by being dripped after succinonitrile -5wt% two (trimethyl fluoride sulfonyl) imine lithium (SN-5wt%LITFSI) heating melting One drips in the flexibility anode thin film, so that the mass ratio of electrolytic salt and organic fibrous material in solid-state anode composite material For 1:6, scanning electron microscope (SEM) photograph is shown in Figure 6, and the flexible solid anode thin film application after SN-5wt%LITFSI is added dropwise Also show good chemical property in solid lithium battery, cycle performance is as shown in Figure 7.

Embodiment 2

The commercially available polytetrafluoroethylene (PTFE) of about 1g (PTFE) is dissolved in the N methyl pyrrolidone of about 10g, polytetrafluoroethyl-ne is obtained Alkene solution.The commercially available, granular size by about 0.8g is commercially available, granular size is about 700nm iron phosphate powder and about 0.14g About the granular size of the Ketjen black of 30~45nm and 0.2g be about 300~450nm the fast conductor lithium lanthanum zirconium tantalum oxygen of lithium ion (LLZTO) it is added in the ethyl alcohol that about 20g contains about 1wt% surfactant and is dispersed with stirring to obtain mixed dispersion liquid.About Spinning is carried out under the high pressure of 15KV simultaneously with by spraying, distance of two syringe needles apart from roller reception device is about 5cm, spinning syringe needle The flow velocity of middle polytetrafluoroethylsolution solution is about 10 μ l/min, and the flow velocity of mixed dispersion liquid is about 100 μ l/min in spraying syringe needle, such as After this work about 8 hours, a flexible solid anode thin film can be taken off from roller reception device, change film at about 1MPa It with a thickness of 100 μm after being rolled about 1 minute, impregnates 24 minutes and dries in lithium perchlorate/ethanol solution later, so that solid The mass ratio of electrolytic salt and organic fibrous material in state anode composite material is 1:3, and it is just very thin to can be prepared by flexible solid Film, ionic conductivity 1.0x10^-3S/cm, density 2.8g/cm³, wherein the content of lithium iron phosphate anode active material reaches To about 80wt%.Scanning electron microscope (SEM) photograph by flexible solid anode thin film manufactured in the present embodiment is shown in Figure 8, charge and discharge for the first time Electric curve is as shown in Figure 9.

Embodiment 3

The commercially available polyacrylonitrile of about 1g (PAN) powder is dissolved in the n,N-Dimethylformamide (DMF) of about 10g, is obtained To polyacrylonitrile solution.By about 1g nickel ion doped (LiNi_0.5Mn_0.5O₂) powder and the commercially available Ketjen black of 0.14g be added to about 20g In ethyl alcohol containing about 1wt% surfactant and it is dispersed with stirring to obtain mixed dispersion liquid.Under the high pressure of about 15KV simultaneously with shoulder Shoulder parallel fashion carries out spinning with by spraying simultaneously, and distance of two syringe needles apart from roller reception device is about 15cm, spinning syringe needle The flow velocity of middle polyacrylonitrile solution is about 10 μ l/min, and the flow velocity of mixed dispersion liquid is about 70 μ l/min in spraying syringe needle, so After work about 16 hours, a flexible solid anode thin film can be taken off from roller reception device, rolled at about 1MPa It impregnates 1 minute and dries in lithium perchlorate/ethanol solution later with a thickness of 250 μm within pressure about 1 minute, so that solid-state anode is multiple The mass ratio of electrolytic salt and organic fibrous material in condensation material is 1:5, can be prepared by flexible solid anode thin film, ion Conductivity is 1.0x10^-4S/cm, density 3.8g/cm³, wherein the content of nickel ion doped is about 85wt%.By the present embodiment system The scanning electron microscope (SEM) photograph of standby flexible solid anode thin film is shown in Figure 10, and first charge-discharge curve is as shown in figure 11.

Embodiment 4

The commercially available Kynoar of about 0.4g (PVDF) powder is dissolved in the N-Methyl pyrrolidone of about 10g, is obtained Kynoar solution.Nickle cobalt lithium manganate Li (NiCoMn) O that commercially available, granular size is about 5 μm by about 1g₂Powder peace treaty The acetylene black that 0.15g is commercially available, granular size is about 30~45nm is added to about 20g and contains about 0.1wt% surfactant In acetone and it is dispersed with stirring to obtain mixed dispersion liquid.Carry out spinning and spraying simultaneously under the high pressure of about 50KV, two syringe needles away from It is about 20cm with a distance from roller reception device, the flow velocity of Kynoar solution is about 200 μ l/min in spinning syringe needle, spraying The flow velocity of mixed dispersion liquid is about 2 μ l/min in syringe needle, after so work about 15 hours, can be taken off from roller reception device One flexible solid anode thin film, then being rolled at about 10MPa about 5 minutes can be prepared by the flexibility with a thickness of 200 μm Solid-state anode thin film, wherein the content of inorganic positive electrode active materials particle nickle cobalt lithium manganate reaches about 95wt%.In addition, will Two (trimethyl fluoride sulfonyl) imine lithium-ethanol solutions of 1mol/L are dripped in the flexibility anode thin film and are dried, so that solid-state is just The mass ratio of electrolytic salt and organic fibrous material in the composite material of pole is 1:4, ionic conductivity 1.0x10^-4S/cm, Density is 4.3g/cm³, scanning electron microscope (SEM) photograph is shown in Figure 12.

Embodiment 5

The commercially available polyacrylonitrile of about 1g (PAN) powder is dissolved in the dimethyl sulfoxide of about 10g, it is molten to obtain polyacrylonitrile Liquid.The mangaic acid lithium powder that about 2g is commercially available, granular size is about 700nm is added in about 20g isopropanol and is dispersed with stirring To LiMn2O4 dispersion liquid.Carry out spinning and spraying, two syringe needle distances simultaneously with parallel fashion shoulder to shoulder under the high pressure of about 5KV The distance of roller reception device is about 5cm, and the flow velocity of polyacrylonitrile solution is about 10 μ l/min in spinning syringe needle, in spraying syringe needle The flow velocity of LiMn2O4 dispersion liquid is about 500 μ l/min, after so work about 30 hours, can take one off from roller reception device Flexible solid anode thin film, the film rolled at about 20MPa about 1 minute after with a thickness of 300 μm, later in lithium salt solution It is middle to impregnate 10 minutes and dry, so that the mass ratio of electrolytic salt and organic fibrous material in solid-state anode composite material is 1: 3, it can be prepared by flexible solid anode thin film, ionic conductivity 1.0x10^-4S/cm, density 2.5g/cm³, wherein mangaic acid The content of lithium is about 60wt%.

Embodiment 6

The commercially available polymethyl methacrylate of about 1g (PMMA) is dissolved in the acetonitrile of about 10g, polymethyl is obtained Sour methyl ester solution.The commercially available, granular size by about 1g is commercially available, granular size is about 700nm cobalt acid lithium powder and about 0.14g About the acetylene black of 30~45nm is added in about 20g water and is dispersed with stirring to obtain mixed dispersion liquid.Under the high pressure of about 25KV Spinning is carried out simultaneously with by spraying, and distance of two syringe needles apart from roller reception device is about 30cm, poly- methyl-prop in spinning syringe needle The flow velocity of e pioic acid methyl ester solution is about 10 μ l/min, and the flow velocity of mixed dispersion liquid is about 30 μ l/min, such work in spraying syringe needle Make about 10 hours after, a flexible solid anode thin film can be taken off from roller reception device, then at about 100KPa into It impregnates 24 hours and dries in lithium perchlorate/ethanol solution later, so that solid-state is just with a thickness of 30 μm within row rolling about 60 minutes The mass ratio of electrolytic salt and organic fibrous material in the composite material of pole is 1:5, can be prepared by flexible solid anode thin film, Ionic conductivity is 1.0x10^-4S/cm, density 1.9g/cm³, wherein the content of positive electrode active materials reaches about 30wt%.

Embodiment 7

The commercially available polyacrylonitrile of about 1g (PAN) powder is dissolved in the n,N-Dimethylformamide (DMF) of about 10g, is obtained To polyacrylonitrile solution.By the cobalt acid sodium (Na that about 1g is commercially available, granular size is about 700nm_0.5CoO₂) end is added to about 20g In ethyl alcohol containing about 1wt% surfactant and it is dispersed with stirring to obtain the dispersion liquid of positive electrode active materials.In the height of about 15KV It depresses while carrying out spinning with by spraying, distance of two syringe needles apart from roller reception device is about 6cm, polypropylene in spinning syringe needle The flow velocity of nitrile solution is about 2 μ l/min, and the flow velocity of the dispersion liquid of positive electrode active materials is about 200 μ l/min in spraying syringe needle, such as After this work about 8 hours, a fexible film can be taken off from roller reception device, rolled about at about 5MPa later 5 minutes, it can be prepared by the flexible solid anode thin film with a thickness of 500 μm, wherein the content of positive electrode active materials reaches about Then sodium perchlorate -- the ethanol solution of suitable 0.5M is added dropwise in 50wt% into the flexibility anode thin film, and in heating in vacuum Ethanol solution is removed under state, so that the mass ratio of electrolytic salt and organic fibrous material in solid-state anode composite material is 1: 10, flexible solid anode thin film, ionic conductivity 1.0x10 can be obtained^-4S/cm, density 2.6g/cm³。

Reference examples 1 (positive suspension is without dispersing agent)

The commercially available polyacrylonitrile of about 1g (PAN) powder is dissolved in the n,N-Dimethylformamide (DMF) of about 10g, is obtained To polyacrylonitrile solution.By about 1gNa_0.5CoO₂It is added in about 20g ethyl alcohol and is dispersed with stirring to obtain Na_0.5CoO₂Dispersion liquid.? Carry out with parallel fashion shoulder to shoulder spinning and spraying under the high pressure of about 25KV simultaneously, two syringe needles apart from roller reception device away from From for about 10cm, the flow velocity of polyacrylonitrile solution is about 10 μ l/min in spinning syringe needle, Na in spraying syringe needle_0.5CoO₂Dispersion liquid Flow velocity be about 70 μ l/min, so work about 8 hours after, a flexibility Na can be taken off from roller reception device_0.5CoO₂ Film, wherein Na_0.5CoO₂Content be about 75wt%.But the uniformity of film is very bad, there is particle agglomeration or nothing in many places Grain phenomenon.

Reference examples 2 (shoulder to shoulder to be mutually perpendicular to)

The commercially available Kynoar of about 1g (PVDF) powder is dissolved in the n,N-Dimethylformamide (DMF) of about 10g, Obtain Kynoar solution.The nickel ion doped that commercially available, granular size is about 0.5 micron by about 1g is added to about 20g and contains In the ethyl alcohol of about 0.1wt% surfactant and it is dispersed with stirring to obtain nickel ion doped dispersion liquid.Two under the high pressure of about 25KV Spray head carries out spinning with by spraying simultaneously in the form of orthogonal, and distance of two spray heads apart from roller reception device is about 10cm, the flow velocity of Kynoar solution is about 10 μ l/min in spinning nozzle, the stream of nickel ion doped dispersion liquid in spraying syringe needle Speed is about 70 μ l/min, after so work about 10 hours, can take a flexible anode thin film off from roller reception device, The content of middle nickel ion doped is 60wt% and uniformity is poor.By the scanning electron microscope (SEM) photograph of flexible anode thin film prepared by this comparative example It is shown in Figure 13.

Reference examples 3 (spinning together after polymer and positive electrode active materials are compound)

By the commercially available Kynoar of 1g (PVDF) powder and 1g, commercially available, granular size is about 0.5 micron to the prior art Nickel ion doped powder be distributed in n,N-Dimethylformamide (DMF), long agitation is uniform, and uniformly mixed solution is existed Spinning is carried out under the high pressure of about 15KV, distance of the spray head apart from roller reception device is about 8cm, and anode mixing is molten in spinning nozzle The flow velocity of liquid is about 15 μ l/min, after so work about 20 hours, can take a film off from roller reception device, then It is rolled at about 1000KPa about 10 minutes, obtained film porosity is higher, inorganic particle solid content about 50%.

Reference examples 4 (blade coating)

The commercially available Kynoar of 1g (PVDF) powder and 1g will commercially available, granular size be about 0.5 micro- by the prior art Rice nickel ion doped powder be distributed in n,N-Dimethylformamide (DMF), long agitation is uniform, then select blade coating or The method of curtain coating prepares anode thin film, but the anode thin film positive electrode dispersion of such method preparation is uneven and pole piece electricity Conductance is lower.

Pass through embodiment 1-7 and reference examples 1-4, it is found that by the obtained flexibility of above-mentioned technical proposal of the invention The ionic conductance of solid-state anode thin film is high (reaching electrochemical device application demand), while having special mechanical property, curved Roll over not broken, machinability is good, shows good chemical property in secondary cell application.

In addition, inventor also refers to the mode of embodiment 1- embodiment 7, with the other raw materials listed in this specification It is tested with condition etc., and the flexibility that high ionic conductance, mechanical property and electrochemical performance has equally been made is solid State anode thin film.

It should be understood that the technical concepts and features of above-described embodiment only to illustrate the invention, ripe its object is to allow The personage for knowing technique cans understand the content of the present invention and implement it accordingly, and protection model of the invention can not be limited with this It encloses.Any equivalent change or modification in accordance with the spirit of the invention should be covered by the protection scope of the present invention.

Claims

1. a kind of solid-state anode composite material, it is characterised in that include:

Electrolytic salt, is distributed in inside the organic fibrous material and the organic fibrous material is constituted with positive electrode active materials Network structure contained by hole；

It can choose addition or the electronic conductor additive not added, Dispersed precipitate is in the solid-state anode composite material； And

It can choose addition or the inorganic ions conductor additive not added, Dispersed precipitate is in the solid-state anode composite material It is interior；

2. solid-state anode composite material according to claim 1, characterized by comprising:

The electrolytic salt being scattered in hole contained by the network structure that the organic fibrous material and positive electrode active materials are constituted.

3. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the organic fibrous material also has There is electronic conductor function.

4. solid-state anode composite material according to claim 1 or 2, which is characterized in that the solid-state anode composite material It further include Dispersed precipitate in the electronic conductor additive in the solid-state anode composite material.

5. solid-state anode composite material according to claim 1 or 2, which is characterized in that the solid-state anode composite material It further include Dispersed precipitate in the inorganic ions conductor additive in the solid-state anode composite material.

6. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the solid-state anode composite material With a thickness of 50~300 μm, preferably 150~250 μm.

7. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the solid-state anode composite material Ionic conductivity be 1.0x10^-4~1.0x10^-2S/cm, ionic conductivity is 1.0x10 at 25 DEG C^-4~1.0x10^-2S/cm。

8. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the solid-state anode composite material Density be 1~5g/cm³, bend resistance intensity is 1~20MPa.

9. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the solid-state anode composite material The mass ratio of Inner electrolysis matter salt and organic fibrous material is 1:2~1:10, preferably 1:3~1:6.

10. solid-state anode composite material according to claim 9, it is characterised in that: in the solid-state anode composite material The content of electrolytic salt is 1~10wt%, preferably 1~5wt%.

11. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the electrolytic salt includes lithium Salt, sodium salt, magnesium salts or aluminium salt；Preferably, the lithium salts includes double trifluoromethanesulfonimide lithiums, lithium perchlorate, hexafluoroarsenate Any one in lithium, lithium hexafluoro phosphate and the bis- trifluoromethanesulfonimide lithiums of succinonitrile-or two or more combinations.

12. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the solid-state anode composite material The diameter of interior organic fibrous material is 50nm~2 μm, preferably 100nm~1 μm, especially preferably 150nm~800nm, especially Preferably 300nm~600nm.

13. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the solid-state anode composite material The content of interior organic fibrous material is 5~60wt%, preferably 10~20wt%.

14. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the material of the organic fibrous material Matter includes polymer；Preferably, the polymer includes polyacrylonitrile, polyethylene oxide, polyvinylpyrrolidone, poly- second two Any one in alcohol, polymethyl methacrylate, Kynoar and polytetrafluoroethylene (PTFE) or two or more combinations；It is preferred that , the organic fibrous material include conducting polymer with it is leading the formation of ionomer blend graft and have simultaneously ion and The polymer of electronic conductor function.

15. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the solid-state anode composite material The content of interior positive electrode active materials be 30~95wt%, preferably 50~90wt%, especially preferably 60~80wt%, it is especially excellent It is selected as 70~80wt%.

16. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the grain of the positive electrode active materials Diameter is 2nm~20 μm, preferably 5nm~10 μm, especially preferably 10nm~5 μm, especially preferably 20nm~1 μm.

17. solid-state anode composite material according to claim 1 or 2, it is characterised in that: the material of the positive electrode active materials Matter include in oxide anode material, sulfide positive electrode and polyanion positive electrode any one or any one It is any in presoma and/or sodium-ion battery positive material, anode of magnesium ion battery material and aluminium ion cell positive material A kind of or any one presoma；Preferably, the material of the positive electrode active materials includes LiFePO4, LiMn2O4, cobalt acid Any one in lithium and nickel ion doped or two or more combinations.

18. solid-state anode composite material according to claim 4, it is characterised in that: in the solid-state anode composite material The content of electronic conductor additive is 0~50wt%, preferably 0~20wt%, especially preferably 0~10wt%；And/or institute State electronic conductor additive include acetylene black, Super P conductive black, Ketjen black, carbon nanotube, carbon fiber, in electrically conductive graphite Any one or two or more combinations.

19. solid-state anode composite material according to claim 5, it is characterised in that: in the solid-state anode composite material The content of inorganic ions conductor additive is 0~70wt%, preferably 0~40wt%, especially preferably 0~20wt%；With/ Or, the inorganic ions conductor additive includes lithium ion conductor additive, sodium ion conductor additive, the addition of magnesium ion conductor Agent or aluminium ion conductor additive, wherein the lithium ion conductor additive includes NASICON type lithium ceramic electrolyte, calcium titanium Mine type lithium ceramic electrolyte, carbuncle type lithium ceramic electrolyte, LISICON type lithium ceramic electrolyte, Li₃The electrolysis of N-type lithium ceramics Matter, lithiumation BPO₄Lead lithium ceramic electrolyte and with Li₄SiO₄For in the lithium ceramic electrolyte of parent any one or it is two or more Combination.

20. a kind of solid-state anode composite material, it is characterised in that it is mainly by the pressurized processing of composite material, then with electrolytic salt It is formed after solution dipping；

The composite material includes:

Continuous organic phase, the continuous organic phase are that polymer solution is ejected on selected receiving plane using electrostatic spinning technique Forming continuous two dimension or three-dimensional structure, the organic fibrous material at least has the function of ion conductor；

While spraying the polymer solution, using electrostatic Spraying technique by the dispersion liquid or anode of positive electrode active materials The mixed dispersion liquid of active material and electronic conductor additive and/or inorganic ions conductor additive is ejected into the selected reception The network structure formed on face,

Wherein, the positive electrode active materials are distributed in hole contained by the continuous organic phase, the electrolytic salt distribution The hole contained by the network structure that the organic fibrous material inside and the organic fibrous material and positive electrode active materials are constituted In hole；

Wherein, if the electronic conductor additive and/or inorganic ions conductor additive exist, the electronic conductor additive And/or inorganic ions conductor additive Dispersed precipitate is in the solid-state anode composite material；

21. solid-state anode composite material according to claim 20, characterized by comprising:

22. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the organic fibrous material is also Has the function of electronic conductor.

23. the solid-state anode composite material according to claim 20 or 21, which is characterized in that the solid-state anode composite wood Material further includes Dispersed precipitate in the electronic conductor additive in the solid-state anode composite material.

24. the solid-state anode composite material according to claim 20 or 21, which is characterized in that the solid-state anode composite wood Material further includes Dispersed precipitate in the inorganic ions conductor additive in the solid-state anode composite material.

25. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the solid-state anode composite wood Material with a thickness of 50~300 μm, preferably 150~250 μm.

26. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the solid-state anode composite wood The ionic conductivity of material is 1.0x10^-4~1.0x10^-2S/cm, ionic conductivity is 1.0x10 at 25 DEG C^-4~1.0x10^-2S/ cm。

27. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the solid-state anode composite wood The density of material is 1~5g/cm³, bend resistance intensity is 1~20MPa.

28. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the solid-state anode composite wood The mass ratio for expecting Inner electrolysis matter salt and organic fibrous material is 1:2~1:10, preferably 1:3~1:6.

29. solid-state anode composite material according to claim 29, it is characterised in that: in the solid-state anode composite material The content of electrolytic salt is 1~10wt%, preferably 1~5wt%.

30. the solid-state anode composite material according to claim 21 or 22, it is characterised in that: the electrolytic salt includes lithium Salt, sodium salt, magnesium salts or aluminium salt；Preferably, the lithium salts includes double trifluoromethanesulfonimide lithiums, lithium perchlorate, hexafluoroarsenate Any one in lithium, lithium hexafluoro phosphate and the bis- trifluoromethanesulfonimide lithiums of succinonitrile-or two or more combinations.

31. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the solid-state anode composite wood The diameter of organic fibrous material is 50nm~2 μm in expecting, preferably 100nm~1 μm, especially preferably 150nm~800nm, especially It is preferably 300nm~600nm.

32. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the solid-state anode composite wood The content of organic fibrous material is 5~60wt%, preferably 10~20wt% in expecting.

33. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the organic fibrous material Material includes polymer；Preferably, the polymer includes polyacrylonitrile, polyethylene oxide, polyvinylpyrrolidone, poly- second two Any one in alcohol, polymethyl methacrylate, Kynoar and polytetrafluoroethylene (PTFE) or two or more combinations；It is preferred that , the organic fibrous material include conducting polymer with it is leading the formation of ionomer blend graft and have simultaneously ion and The polymer of electronic conductor function.

34. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the solid-state anode composite wood Expect in positive electrode active materials content be 30~95wt%, preferably 50~90wt%, especially preferably 60~80wt%, especially Preferably 70~80wt%.

35. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the positive electrode active materials Partial size is 2nm~20 μm, preferably 5nm~10 μm, especially preferably 10nm~5 μm, especially preferably 20nm~1 μm.

36. the solid-state anode composite material according to claim 20 or 21, it is characterised in that: the positive electrode active materials Material include in oxide anode material, sulfide positive electrode and polyanion positive electrode any one or any one Presoma and/or sodium-ion battery positive material, anode of magnesium ion battery material and aluminium ion cell positive material in appoint One kind of anticipating or the presoma of any one；Preferably, the material of the positive electrode active materials includes LiFePO4, LiMn2O4, cobalt Any one in sour lithium and nickel ion doped or two or more combinations.

37. solid-state anode composite material according to claim 23, it is characterised in that: in the solid-state anode composite material The content of electronic conductor additive is 0~50wt%, preferably 0~20wt%, especially preferably 0~10wt%；And/or institute State electronic conductor additive include acetylene black, Super P conductive black, Ketjen black, carbon nanotube, carbon fiber, in electrically conductive graphite Any one or two or more combinations.

38. solid-state anode composite material according to claim 24, it is characterised in that: in the solid-state anode composite material The content of inorganic ions conductor additive is 0~70wt%, preferably 0~40wt%, especially preferably 0~20wt%；With/ Or, the inorganic ions conductor additive includes lithium ion conductor additive, sodium ion conductor additive, the addition of magnesium ion conductor Agent or aluminium ion conductor additive, wherein the lithium ion conductor additive includes NASICON type lithium ceramic electrolyte, calcium titanium Mine type lithium ceramic electrolyte, carbuncle type lithium ceramic electrolyte, LISICON type lithium ceramic electrolyte, Li₃The electrolysis of N-type lithium ceramics Matter, lithiumation BPO₄Lead lithium ceramic electrolyte and with Li₄SiO₄For in the lithium ceramic electrolyte of parent any one or it is two or more Combination.

39. solid-state anode composite material according to claim 20, it is characterised in that: quiet in the electrostatic spinning technique The spacing of Electrospun liquid outlet and the receiving plane is 5~30cm, and electrostatic potential is 5~50KV；And/or the electrostatic spray In technology, the spacing of electrostatic spray liquid outlet and the receiving plane is 5~30cm, and electrostatic potential is 5~50KV.

40. solid-state anode composite material according to claim 39, it is characterised in that: the spray of the electrostatic spinning liquid outlet The injection direction of direction and the electrostatic spray liquid outlet is penetrated into the angle less than 90 ° more than or equal to 0.

41. solid-state anode composite material according to claim 20, it is characterised in that: the polymer solution and it is described just The flow-rate ratio of the dispersion liquid of pole active material or the mixed dispersion liquid be 100:1~1:100, preferably 1:10~1:50, especially It is preferably 1:3~1:7.

42. solid-state anode composite material according to claim 20, it is characterised in that: the pressure of the pressurized treatments is 100KPa~20MPa, time are 1~60 minute, and preferably 1~10 minute, temperature was 25~60 DEG C；And/or the dipping Time is 1 minute~24 hours, preferably 5~10 minutes.

43. a kind of solid-state anode, including plus plate current-collecting body, it is characterised in that: be covered with claim on the plus plate current-collecting body Solid-state anode composite material described in any one of 1-42.

44. solid-state anode according to claim 43, it is characterised in that: the plus plate current-collecting body includes aluminium foil, utter misery aluminium Any one of foil, carbon felt, carbon paper；And/or the solid-state anode composite material is uniformly covered in plus plate current-collecting body surface, and The solid-state anode composite material with a thickness of 10~300 μm, preferably 30~250 μm, especially preferably 50~100 μm, Ionic conductivity is 1.0x10 at 25 DEG C^-4~1.0x10^-2S/cm。

45. a kind of preparation method of solid-state anode composite material, characterized by comprising:

Polymer solution is ejected on selected receiving plane using electrostatic spinning technique and forms continuous two dimension or three-dimensional structure, The organic fibrous material at least has the function of ion conductor；

While spraying the polymer solution, using electrostatic Spraying technique by the dispersion liquid or anode of positive electrode active materials The mixed dispersion liquid of active material and electronic conductor additive and/or inorganic ions conductor additive is ejected into the selected reception On face, obtained composite material progress pressurized treatments are made into its densification later, the positive electrode active materials is made to be distributed in the company In hole contained by continuous organic phase, then with the electrolyte salt solution dipping composite material, enter electrolytic salt described multiple Contained by the network structure that organic fibrous material inside and the organic fibrous material and positive electrode active materials in condensation material are constituted Hole in, form the solid-state anode composite material；

46. preparation method according to claim 45, characterized by comprising: will be used to spray the polymer solution The electrostatic spray of electrostatic spinning liquid outlet and dispersion liquid or the mixed dispersion liquid for spraying the positive electrode active materials Liquid outlet is arranged in parallel in the form of in harness.

47. preparation method according to claim 46, characterized by comprising: make the injection of the electrostatic spinning liquid outlet The injection direction of direction and the electrostatic spray liquid outlet is at the angle less than 90 ° more than or equal to 0.

48. the preparation method according to claim 46 or 47, it is characterised in that: the electrostatic spinning liquid outlet and/or quiet The shape of electron spray liquid outlet includes round or slit shape.

49. preparation method according to claim 45, it is characterised in that: the dispersion liquid of the positive electrode active materials or institute Stating mixed dispersion liquid also includes surfactant；Preferably, dispersion of the surfactant in the positive electrode active materials Content in liquid or the mixed dispersion liquid is 0.1~1wt%；Especially preferred, the surfactant includes ionic Surfactant, nonionic surface active agent, amphoteric surfactant, any one or two kinds in compound surfactant Above combination；Especially preferred, the ionic surfactant includes cationic surfactant and/or anionic surface Activating agent.

50. preparation method according to claim 45, it is characterised in that further include: the receiving plane and electrostatic spinning of Yu Suoshu Apply extra electric field between liquid outlet and/or electrostatic spray liquid outlet.

51. preparation method according to claim 45, it is characterised in that: the receiving plane is the surface of reception device；It is excellent Choosing, the reception device include in roller reception device, plane reception device and aqueous solution reception device any one or Two or more combinations；Preferably, the receiving plane is provided with negative electrical charge generating device.

52. preparation method according to claim 45, it is characterised in that: the polymer solution and the anode is living When the dispersion liquid of property material or the mixed dispersion liquid are sprayed to the receiving plane, the electrostatic spinning liquid outlet and electrostatic Along the axial relative movement of the reception device between mist liquid outlet and the receiving plane.

53. preparation method according to claim 45, it is characterised in that: the polymer solution and the anode is living When the dispersion liquid of property material or the mixed dispersion liquid are sprayed to the receiving plane, the electrostatic spinning liquid outlet and electrostatic Length direction or width direction between mist liquid outlet and the receiving plane along the receiving plane carry out reciprocal relative motion.

54. preparation method according to claim 51, it is characterised in that: the polymer solution and the anode is living Property material dispersion liquid or mixed dispersion liquid when being sprayed to the cylinder surface of the roller reception device, the roller is protected Hold rotation status；Preferably, the revolving speed of the roller reception device is 300~1000rpm.

55. preparation method according to claim 45, it is characterised in that: the polymer solution and the anode is living Property material dispersion liquid or mixed dispersion liquid when being sprayed to the receiving plane, the polymer solution and the positive-active The flow-rate ratio of the dispersion liquid of material or the mixed dispersion liquid be 100:1~1:100, preferably 1:10~1:50, particularly preferably For 1:3~1:7.

56. preparation method according to claim 46, it is characterised in that: the electrostatic spinning liquid outlet and electrostatic spray go out The spacing of liquid mouth and the receiving plane is 5~30cm；And/or the electrostatic spinning technique and electrostatic Spraying technique use it is quiet Piezoelectric voltage is 5~50KV.

57. preparation method according to claim 45, it is characterised in that: the pressure of the pressurized treatments be 100KPa~ 20MPa, time are 1~60 minute, and preferably 1~10 minute, temperature was 25~60 DEG C；And/or the time of the dipping is 1 Minute~24 hours, preferably 5~10 minutes.

58. preparation method according to claim 45, it is characterised in that: the electrolytic salt includes lithium salts, sodium salt, magnesium salts Or aluminium salt；Preferably, the lithium salts includes double trifluoromethanesulfonimide lithiums, lithium perchlorate, hexafluoroarsenate lithium, lithium hexafluoro phosphate With any one or the two or more combinations in the bis- trifluoromethanesulfonimide lithiums of succinonitrile-.

59. preparation method according to claim 45, characterized by comprising: it dissolves the polymer in the first solvent, Obtain the polymer solution.

60. preparation method according to claim 59, it is characterised in that: the polymer includes polyacrylonitrile, polycyclic oxygen It is any in ethane, polyvinylpyrrolidone, polyethylene glycol, polymethyl methacrylate, Kynoar and polytetrafluoroethylene (PTFE) A combination of one or more；Preferably, the polymer includes conducting polymer and leads ionomer blend graft shape At and there is the polymer of ion and electronic conductor function simultaneously；And/or first solvent includes water, N- methylpyrrole Alkanone, alcohol, n,N-Dimethylformamide, dimethyl sulfoxide, any one or two or more combinations in dimethyl acetamide； Preferably, the alcohol includes ethyl alcohol.

61. preparation method according to claim 45, characterized by comprising: positive electrode active materials are dispersed in In two solvents, the dispersion liquid of the positive electrode active materials is obtained；

Alternatively, positive electrode active materials and electronic conductor additive and/or inorganic ions conductor additive are dispersed in second In solvent, the mixed dispersion liquid is obtained.

62. preparation method according to claim 61, it is characterised in that: the material of the positive electrode active materials includes oxidation Any one or any one presoma in object positive electrode, sulfide positive electrode and polyanion positive electrode and/ In sodium-ion battery positive material, anode of magnesium ion battery material and aluminium ion cell positive material any one or it is any A kind of presoma；Preferably, the material of the positive electrode active materials includes LiFePO4, LiMn2O4, cobalt acid lithium and nickel mangaic acid Any one in lithium or two or more combinations；

And/or the electronic conductor additive includes acetylene black, Super P conductive black, Ketjen black, carbon nanotube, carbon fiber Any one in dimension, electrically conductive graphite or two or more combinations；

And/or the inorganic ions conductor additive includes lithium ion conductor additive, sodium ion conductor additive, magnesium ion Conductor additive or aluminium ion conductor additive, wherein the lithium ion conductor additive includes the electrolysis of NASICON type lithium ceramics Matter, Ca-Ti ore type lithium ceramic electrolyte, carbuncle type lithium ceramic electrolyte, LISICON type lithium ceramic electrolyte, Li₃N-type lithium pottery Porcelain electrolyte, lithiumation BPO₄Lead lithium ceramic electrolyte and with Li₄SiO₄For in the lithium ceramic electrolyte of parent any one or two Kind or more combination；

And/or second solvent includes water, alcohol, any one or two or more combinations in ketone；Preferably, the alcohol Including ethyl alcohol and/or isopropanol；Preferably, the ketone includes acetone.

63. a kind of preparation method of solid-state anode, characterized by comprising: according to described in any one of claim 45-62 Method prepares solid-state anode composite material, and the solid-state anode composite material is uniformly covered on plus plate current-collecting body, obtains Solid-state anode.

64. described in any one of solid-state anode composite material or claim 43-44 described in any one of claim 1-42 Solid-state anode or any one of claim 45-62 the method preparation solid-state anode composite material or claim 63 institute The solid-state anode stated is in preparing the purposes in electrochemical device.

65. purposes according to claim 64, it is characterised in that: the electrochemical device includes energy storage device and/or electricity Mutagens color device；Preferably, the energy storage device includes battery；Preferably, the electrochromic device includes e-book；Especially Preferably, the e-book includes black and white e-book and/or color e-book.