CN108183257A

CN108183257A - Organogel electrolyte, application, sodium base double ion organic solid-state battery and preparation method thereof

Info

Publication number: CN108183257A
Application number: CN201711440243.7A
Authority: CN
Inventors: 唐永炳; 于奥; 张苗
Original assignee: Shenzhen Institute of Advanced Technology of CAS
Current assignee: Shenzhen Institute of Advanced Technology of CAS
Priority date: 2017-12-26
Filing date: 2017-12-26
Publication date: 2018-06-19

Abstract

The invention discloses a kind of organogel electrolyte, application, sodium base double ion organic solid-state battery and preparation method thereof, are related to electrochemical energy storing device field.Organogel electrolyte includes electrolyte sodium salt, nonaqueous solvents and organic polymer.Sodium base double ion organic solid-state battery includes cathode, anode, diaphragm and organogel electrolyte；Cathode is can be with sodium ion alloyed metal (AM), metal alloy or metal composite；Anode includes plus plate current-collecting body and positive electrode, and active substances in cathode materials is can reversibly be embedded in, the stratified material of deintercalation sodium salt anion.The present invention alleviates the problem of organic electrolyte is volatile, inflammable, explosive and sodium ion solid state battery is led ionic nature and electric conductivity and cannot be had both, and security performance is bad under high temperature.Organogel electrolyte of the present invention has good diversion and electric conductivity, can alleviate the pole piece pulverizing problem caused by the volume expansion that alloying is brought, and the cyclical stability of battery and has a safety feature.

Description

Organogel electrolyte, application, sodium base double ion organic solid-state battery and its preparation Method

Technical field

The present invention relates to electrochemical energy storing device technical fields, in particular to a kind of organogel electrolyte, answer With, sodium base double ion organic solid-state battery and preparation method thereof.

Background technology

Lithium ion battery have energy density is high, energy efficiency is high, have extended cycle life, memory-less effect, repid discharge etc. Advantage, thus have in the fields such as consumption electronic product and electric vehicle, peak load regulation network, accumulation power supply, aerospace huge The market demand.Though the organic electrolyte used in traditional lithium ion battery is with very high ionic conductivity, electrode/electrolyte circle The advantages that face is easy to control, working process facilitates, but organic electrolyte is volatile, inflammable, explosive so that battery especially large capacity When there are larger security risk, in addition limited electrochemical window causes it to encounter many difficulties in high-voltage battery system. And it is expected to preferably improve battery security and realize using the solid state battery that the solid electrolyte of high ionic conductivity is formed High energy density, in recent years by the concern of domestic and international researcher and attention.Usual solid electrolyte can be divided by its chemical composition For following three classes：Inorganic type solid electrolyte, solid polyelectrolyte and composite solid electrolyte.

Due to lithium ion battery there are shortage of resources, lithium cost recovery is high, lithium battery cost of manufacture is high the problem of, went out later Sodium-ion battery is showed.Mainly based on high temperature sodium-sulfur battery, sodium-sulfur battery mainly uses existing solid-state sodium-ion battery Sodium ion ceramics are as electrolyte (with Na- β-Al₂O₃Based on).β-Al₂O₃Ceramics are the polycrystalline material Na with layered structure₂O- 11Al₂O₃As the electrolyte of leading electric material, the Na of internal defect₂O is by fine and close Al₂O₃It successively separates, the conductance at 300 DEG C Rate is up to 1.3 × 10^-1S/cm.Researcher in 2014 is prepared for sodium ion ceramic electrolyte Na using high-temperature melting method₂B₁₂H₁₂, And it confirms that internal resistance is smaller at a certain temperature for the sodium ion ceramics, is conducive to the transmission of ion.But ceramic electrolyte remains unchanged Be faced with that temperature in use is excessively high and the safety issue brought.The shortcomings that existing all-solid sodium ion battery, has：(1) material is more It is synthesized using the methods of traditional sol-gel method, fusion method, mortar sintering, obtained sample is impure, and component is difficult to control； (2) fast-ionic conductor that synthesis obtains is difficult to find the electrode to match therewith, and it typically belongs to structural unstable pure crystalline substance Body, aerial unstable chemcial property are difficult to realize large-scale application；(3) at room temperature, the electricity of all solid state electrolyte Conductance is smaller, there is preferable electric conductivity under high temperature, however, there are safety issues under high temperature.

CN106532114A proposes a kind of sodium ion solid state electrolysis composite material and its system based on NASICON structures Preparation Method and application are to have synthesized a kind of consolidating based on NASICON structures using traditional sol-gel method in the patent of invention Body electrolyte composite material, obtained composite solid electrolyte at room temperature ionic conductivity up to 3.4 × 10^-3S/cm, patent Starting point is the preparation of fast-ionic conductor, and what is more considered is the ionic nature of leading of solid electrolyte, but shortcoming is electric conductivity It is poor.

With reference to sodium ion and the overall merit of Dual-ion cell, Tang Yong Ping and its team propose a kind of completely new based on sodium The novel high-performance of ion electrolyte, inexpensive tin-graphite Dual-ion cell improve the energy density of sodium-ion battery, together When reduce the production cost of battery.But tinfoil paper as cathode when there is also some problems：(1) sodium ion is closed with tin metal Huge volume expansion is undergone during aurification, causes electrode dusting that battery capacity is caused to decay；(2) metallic tin exists with electrolyte The interface solid electrolyte layer to be formed (SEI films) that reacts constantly thickens at any time, and interface impedance is continuously increased, coulombic efficiency It reduces, battery capacity attenuation；(3) since tin metal negative electrode volume constantly changes in charge and discharge process, SEI films are unstable, During deintercalation sodium, continuous generation-rupture-regeneration consumes metallic sodium and electrolyte；(4) traditional secondary cell is adopted more With liquid organic electrolyte, the problems such as being susceptible to leakage, electrode corrosion, can even explode under high temperature.It is asked for these Topic, researcher are modified to solve the volume expansion brought when alloying occurs also by tinfoil paper is carried out on certain surface With the pole piece pulverizing problem in charge and discharge process, by adding in a variety of different film for additive into electrolyte to promote in tin Foil surface forms form compact and stable SEI films, so as to reduce the capacity attenuation in cyclic process to a certain extent；Or to electricity It solves and initiator, crosslinking agent etc. is added in liquid, make the organic monomer in electrolyte that polymerisation occur under certain condition and coagulated Glue electrolyte, so as to solve the problems, such as electrolyte interface side reaction.Although these modes improve to a certain extent sodium from The chemical property of sub- battery, but the problem of new is brought simultaneously：All it is investigating in inorganic compound level as surface is modified, Or it forms SEI films and the situation of rupture is still had in cyclic process or adds in initiator or crosslinking agent generation polymerization instead It should be there may be heat expansion, hot drum phenomenon, so as to influence battery performance.

In view of this, it is special to propose the present invention.

Invention content

One of the objects of the present invention is to provide a kind of organogel electrolyte, which leads ensure that While ionic nature, inheriting the good advantage of liquid conductive and preferable mechanical strength and flexibility, gel electrolyte has Better security performance.

The second object of the present invention is to provide a kind of organogel electrolyte in sodium base Dual-ion cell Using, above-mentioned organogel electrolyte is applied to improve circulating battery stability and service life in sodium base Dual-ion cell, Battery remains to keep the performance of good electric conductivity and diversion at room temperature, improves the security performance of battery.

The third object of the present invention is to provide a kind of sodium base double ion including the organogel electrolyte organic Solid state battery has the advantage same with above-mentioned organogel electrolyte phase.It is organic a kind of sodium base double ion has been preferably provided simultaneously Solid state battery, the advantages of combining sodium-ion battery and Dual-ion cell respectively, with can be with sodium ion alloyed metal (AM), gold Belong to alloy or metal composite as negative material and collector, can reversibly be embedded in, the stratiform of deintercalation sodium salt anion For material as active substances in cathode materials, the organogel to contain sodium salt has the electrolysis of above-mentioned organogel as electrolyte The advantage of matter, the volume expansion that is brought due to alloying can be alleviated and caused by pole piece pulverizing problem, so as to improve battery Cyclical stability, realize the long lifetime of battery；Positive and negative pole material is simple, is easy to get, is environmentally friendly, safety；Organic electrolyte has Flexibility well, has widened the application field of battery；Battery remains to keep at room temperature good electric conductivity and diversion Performance so as to reduce the temperature in use of battery, substantially increases the security performance of battery.

The fourth object of the present invention is to provide a kind of preparation method of sodium base double ion organic solid-state battery, described will bear Pole, organogel electrolyte, diaphragm, anode are assembled, and preparation process is simple, at low cost.

In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：

In a first aspect, the present invention provides a kind of organogel electrolyte, including electrolyte sodium salt, nonaqueous solvents, organic Polymer and optional additive.

Preferably, on the basis of technical solution of the present invention, organogel electrolyte include mass percent such as the following group Point：Sodium salt 1-50%, nonaqueous solvents 20-85%, organic polymer 1-50% and additive 0.5-10%.

Preferably, electrolyte sodium salt includes sodium hexafluoro phosphate, sodium borohydride, sodium carbonate, sodium bicarbonate, sodium chloride, fluorination Sodium, sodium sulphate, sodium phosphate, sodium nitrate, difluoro oxalate Boratex, sodium pyrophosphate, neopelex, dodecyl sulphate Sodium, sodium citrate, kodalk, Boratex, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, silicic acid Sodium, sodium lignin sulfonate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, hexafluoroarsenate sodium, tetrafluoro boric acid Sodium, sodium perchlorate or one kind in trifluoromethanesulfonimide sodium or at least two；Preferably sodium hexafluoro phosphate；

Preferably, nonaqueous solvents is organic solvent and/or ionic liquid；

Preferably, organic solvent includes esters, sulfone class, ethers, nitrile or one kind in olefines organic solvent or at least Two kinds；And/or

Ionic liquid includes imidazoles, piperidines, pyroles, quaternary amines or one kind in amides ionic liquid or at least Two kinds；

Preferably, organic solvent includes propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, carbonic acid first Ethyl ester, methyl formate, methyl acetate, DMAC N,N' dimethyl acetamide, fluorinated ethylene carbonate, methyl propionate, ethyl propionate, acetic acid Ethyl ester, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- dioxolanes, 4- methyl-1,3-dioxies pentamethylene, Dimethoxymethane, 1,2- diformazans Ethylene Oxide, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, sulfurous acid One kind in acrylic ester, dimethyl sulfite or sulfurous acid diethyl ester or crown ether or at least two, preferably ethylene carbonate, carbon The mixed solvent of dimethyl phthalate and methyl ethyl carbonate；

Preferably, ionic liquid includes 1- ethyl-3-methylimidazoles-hexafluorophosphate, 1- ethyl-3-methylimidazoles-four Borofluoride, 1- ethyl-3-methylimidazoles-bis trifluoromethyl sulfimide salt, 1- propyl -3- methylimidazoles-hexafluorophosphate, 1- propyl -3- methylimidazoles-tetrafluoroborate, 1- propyl -3- methylimidazoles-bis trifluoromethyl sulfimide salt, 1- butyl -1- Methylimidazole-hexafluorophosphate, 1- butyl -1- methylimidazoles-tetrafluoroborate, 1- butyl -1- methylimidazoles-bis trifluoromethyl Sulfimide salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyls sulfimide salt, 1- butyl -1- methylpyrrolidin- double three Methyl fluoride sulfimide salt, N- Methyl-N-propyls pyrrolidines-bis trifluoromethyl sulfimide salt, N- first, propylpiperdine-bis- three One kind or at least two in methyl fluoride sulfimide salt or N- methyl butyls piperidines-bis trifluoromethyl sulfimide salt.

Preferably, on the basis of technical solution of the present invention, organic polymer include polyvinyl chloride, chliorinated polyvinyl chloride, Kynoar, polyacrylonitrile, polyethylene, polypropylene oxide, polymethyl-benzene e pioic acid methyl ester, thermoplastic acrylic resin, polyoxy One kind in ethylene, vinylidene fluoride-hexafluoropropylene copolymer or polystyrene or at least two；Preferably polyoxyethylene-poly- first Base benzene e pioic acid methyl ester copolymer；

Preferably, additive adds including film for additive, additives for overcharge protection additive, stabilizer, improvement high temperature performance Add one kind in agent, conductive additive or flame-retardant additive or at least two；

Preferably, additive includes fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, the third sulphurs of 1,3- Acid lactone, 1,4- butyl sultones, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, sulfurous acid third Enester, dimethyl sulfite, diethyl sulfite, glycol sulfite, methyl chlorocarbonate, dimethyl sulfoxide (DMSO), benzene first Ether, acetamide, diazine, metadiazine, crown ether 12-crown-4, crown ether 18- crown-s 6,4- fluoroanisoles, fluoro chain ether, Difluoromethyl ethylene carbonate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, trifluoro Ethylphosphonic acid, bromo butyrolactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, ethanol amine, carbonization dimethylamine, ring Butyl sulfone, 1,3- dioxolanes, acetonitrile, long-chain olefin, alundum (Al2O3), magnesia, barium monoxide, sodium carbonate, calcium carbonate, two One kind in carbonoxide, sulfur dioxide or lithium carbonate or at least two.

Second aspect, the present invention provides a kind of application of above-mentioned organogel electrolyte in sodium base Dual-ion cell.

The third aspect, the present invention provides a kind of sodium base double ion organic solid-state electricity including above-mentioned organogel electrolyte Pond.

Preferably, a kind of sodium base double ion organic solid-state battery, including cathode, anode, the diaphragm between positive and negative anodes And above-mentioned organogel electrolyte；

The cathode is can be with sodium ion alloyed metal (AM), metal alloy or metal composite；

The anode includes plus plate current-collecting body and positive electrode, and positive electrode includes active substances in cathode materials, anode material Material active material is can reversibly be embedded in, the stratified material of deintercalation sodium salt anion.

Preferably, on the basis of technical solution of the present invention, the cathode for tin, copper, iron, nickel, titanium, aluminium, zinc, manganese, lead, The metal of any one in antimony, cadmium, gold, bismuth or germanium；Or,

The cathode is including at least any one in tin, copper, iron, nickel, titanium, aluminium, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium The alloy of kind；Or,

The cathode is including at least any one in tin, copper, iron, nickel, titanium, aluminium, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium The metal composite of kind；

Preferably, the cathode is tin, tin alloy or stanniferous compound.

Preferably, on the basis of technical solution of the present invention, active substances in cathode materials includes graphite-like carbon material, vulcanization One kind in object, nitride, oxide or carbide material or at least two；

Preferably, graphite-like carbon material includes carbonaceous mesophase spherules graphite, native graphite, expanded graphite, vitreous carbon, carbon carbon Composite material, carbon fiber, hard carbon, porous charcoal, highly oriented graphite, carbon black, carbon nanotube or one kind in graphene or at least two Kind；

Preferably, sulfide includes molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, ferrous disulfide, vulcanization Asia One kind in iron, nickel sulfide, zinc sulphide, cobalt sulfide or manganese sulfide or at least two；

Preferably, nitride includes one or both of hexagonal boron nitride or carbon doping hexagonal boron nitride；

Preferably, oxide includes molybdenum trioxide, tungstic acid, vanadic anhydride, vanadium dioxide, titanium dioxide, oxidation One kind in zinc, copper oxide, nickel oxide or manganese oxide or at least two；

Preferably, carbide includes one kind or at least two in titanium carbide, ramet, molybdenum carbide or silicon carbide.

Preferably, on the basis of technical solution of the present invention, positive electrode includes the positive electrode active matter of 60-90wt% The binding agent of matter, the conductive agent of 5-30wt% and 5-10wt%；

Preferably, conductive agent is in conductive black, conductive carbon ball, electrically conductive graphite, carbon nanotube, carbon fiber or graphene One kind or at least two；

Preferably, binding agent is selected from Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, SBR rubber Or one kind in polyolefins binding agent or at least two；

Preferably, plus plate current-collecting body is any one in aluminium, copper, iron, nickel, titanium, tin, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium The metal of kind；Or, plus plate current-collecting body is including at least in aluminium, copper, iron, nickel, titanium, tin, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium The alloy of any one；Or, plus plate current-collecting body is including at least aluminium, copper, iron, nickel, titanium, tin, zinc, manganese, lead, antimony, cadmium, gold, bismuth Or the metal composite of any one in germanium；Preferably, plus plate current-collecting body is aluminium foil.

Fourth aspect, the present invention provides a kind of preparation method of above-mentioned sodium base double ion organic solid-state battery, by cathode, Organogel electrolyte, diaphragm and anode are assembled, and obtain sodium base double ion organic solid-state battery.

Preferably, on the basis of technical solution of the present invention, the preparation method of sodium base double ion organic solid-state battery, including Following steps：

A) cathode is prepared：It is spare as cathode after the metal, alloy or metal composite of required size are cleaned；

B) organic gel electrolyte is prepared：Sodium salt electrolyte is dissolved in nonaqueous solvents, is added after being sufficiently mixed organic Polymer obtains organogel electrolyte；

C) diaphragm is prepared：Diaphragm is cut into required size, diaphragm is used as after cleaning；

D) anode is prepared：Active substances in cathode materials, conductive agent and binding agent and solvent are mixed and made into slurry；It again will just Pole material paste is evenly applied to plus plate current-collecting body surface, and cut-parts after drying obtain the anode of required size；

The diaphragm and step that organogel electrolyte, the step c) that cathode, the step b) that step a) is obtained are obtained are obtained Rapid anode d) obtained is assembled, and obtains sodium base double ion organic solid-state battery.

Compared with the prior art, the present invention has the advantages that：

(1) organogel electrolyte of the invention ensure that lead ionic nature while, it is good to inherit liquid conductive Advantage, so as to form gel electrolyte that is not only conductive but also having the sodium double ion for leading ionic nature.Organogel electricity Solving matter has good ionic conductivity and ion conduction property, and electronics can be quickly conducted during high power charging-discharging；Have The ion channel of ion can quickly be transmitted by having in machine gel electrolyte, can ensure that ion transmits under high power charging-discharging；Have Machine gel electrolyte has certain mechanical strength, can alleviate electric by the use of metal of alloying as the sodium ion of cathode and collector Volume expansion that pond is brought due to alloying and caused by pole piece pulverizing problem, it is real so as to improve the cyclical stability of battery The long lifetime of existing battery；Organogel electrolyte has good flexibility, available for wearable, flexible apparatus, has widened electricity The application field in pond；Gel solid state electrolyte alleviates conventional organic solution liquid safety that is volatile, inflammable, explosive and bringing and asks Topic, gel electrolyte have better security performance.

(2) organogel electrolyte is applied to that in sodium base Dual-ion cell circulating battery stability can be improved by the present invention And the service life, at room temperature battery remain to keep the performance of good electric conductivity and diversion, improve the security performance of battery.

(3) present invention preferably provides typical sodium base double ion organic solid-state battery with can be with sodium ion alloying Metal, metal alloy or metal composite are as negative material and collector, can reversibly be embedded in, deintercalation sodium salt anion Stratified material as active substances in cathode materials, the organogel to contain sodium salt passes through sodium ion and gold as electrolyte Belong to the storage that energy is realized in insertion, the abjection of the alloying reaction and sodium salt anion of paillon on positive electrode.The sodium base Double ion organic solid-state battery has the advantage of above-mentioned organogel electrolyte, and it is swollen can to alleviate the volume brought due to alloying It is swollen and caused by pole piece pulverizing problem, so as to improve the cyclical stability of battery, realize the long lifetime of battery；Positive and negative anodes material Material is simple, is easy to get, is environmentally friendly, safety；And organic electrolyte has good flexibility, has widened the application field of battery；Sodium base Double ion organic solid-state battery remains to keep at room temperature the performance of good electric conductivity and diversion, so as to reduce battery Temperature in use substantially increases the security performance of battery.

(4) the typical sodium base double ion organic solid-state battery of the present invention combines sodium-ion battery with Dual-ion cell respectively The advantages of, using sodium salt instead of lithium salts, alleviate lithium ion battery shortage of resources, lithium cost recovery height and lithium battery and be fabricated to The problem of this is high.

Description of the drawings

Fig. 1 is the structure diagram of the sodium base double ion organic solid-state battery of one embodiment of the present invention.

Icon：1- negative current collectors；2- gel electrolytes；3- diaphragms；4- positive electrode material layers；5- plus plate current-collecting bodies；6- electricity Pond cathode housing；7- battery cathode housings.

Specific embodiment

Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer is The conventional products that can be obtained by commercially available purchase.

According to the first aspect of the invention, a kind of organogel electrolyte is provided, including electrolyte sodium salt, non-aqueous Agent, organic polymer and optional additive.

Organogel electrolyte includes the nonaqueous solvents containing sodium salt and organic polymer.

Sodium ion and anion double ion derive from sodium salt, and sodium salt is not particularly limited, and are using well known sodium salt It can.

Nonaqueous solvents refers to solvent than water, such as organic solvent, ionic liquid etc..Solvent can make electrolyte sodium salt Sodium ion and anion are dissociated into, and cation and anion can be with free migrations.

Organic polymer can be the substance for having cross-linked gel structure, be mixed to form with nonaqueous solvents gelatinous organic Gel electrolyte.

Organic polymer is not particularly limited, the well known substance in solid electrolyte field can be suitably used.

Typical but non-limiting organic polymer is, for example, polyvinyl chloride, chliorinated polyvinyl chloride, Kynoar, poly- third Alkene nitrile, polyethylene, polypropylene oxide, polymethyl-benzene e pioic acid methyl ester, thermoplastic acrylic resin, polyoxyethylene, vinylidene-six Fluoropropene copolymer or polystyrene etc. preferably select the one or more in these organic polymers.

Additive can carry out selective addition according to demand.

Sodium salt electrolyte liquid electrolyte is converted into gel electrolyte in the present invention, the same of ionic nature is led ensure that When, the good advantage of liquid conductive is inherited, has the solidifying of the sodium double ion for leading ionic nature so as to be formed not only conductive Glue electrolyte.The organogel electrolyte has the following advantages：

(1) there is good ionic conductivity and ion conduction property, can quickly be conducted during high power charging-discharging Electronics；(2) have the ion channel that can quickly transmit ion in organogel electrolyte, can ensure under high power charging-discharging from Son transmission；(3) organogel electrolyte has certain mechanical strength, can alleviate by the use of metal of alloying as cathode and afflux Volume expansion that the sodium-ion battery of body is brought due to alloying and caused by pole piece pulverizing problem, so as to improve following for battery Ring stability realizes the long lifetime of battery；(4) organogel electrolyte has good flexibility, available for wearable, flexible Equipment has widened the application field of battery；(5) it is volatile, inflammable, easy to alleviate conventional organic solution liquid for gel solid state electrolyte The quick-fried and safety problem brought, gel electrolyte have better security performance.

In a preferred embodiment, organogel electrolyte includes the following component of mass percent：Sodium salt 1- 50%th, nonaqueous solvents 20-85%, organic polymer 1-50% and additive 0.5-10%.

Using organogel electrolyte as calculating benchmark, nonaqueous solvents, the 1- of sodium salt, 20-85wt% including 1-50wt% The organic polymer of 50wt% and the additive of 0.5-10wt%.

[sodium salt]

The typical but non-limiting mass percentage of sodium salt is, for example, 1%, 2%, 5%, 10%, 15%, 20%, 25%th, 30%, 35%, 40%, 45% or 50%.

As a preferred embodiment, electrolyte sodium salt includes sodium hexafluoro phosphate, sodium borohydride, sodium carbonate, carbonic acid Hydrogen sodium, sodium chloride, sodium fluoride, sodium sulphate, sodium phosphate, sodium nitrate, difluoro oxalate Boratex, sodium pyrophosphate, detergent alkylate sulphur Sour sodium, lauryl sodium sulfate, sodium citrate, kodalk, Boratex, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, iodine Sour sodium, sodium iodide, sodium metasilicate, sodium lignin sulfonate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, hexafluoro Natrium arsenicum, sodium tetrafluoroborate, sodium perchlorate, one kind in trifluoromethanesulfonimide sodium or at least two；Preferably hexafluoro phosphorus Sour sodium.

[nonaqueous solvents]

The typical but non-limiting mass percentage of nonaqueous solvents is, for example, 20%, 25%, 30%, 35%, 40%, 45%th, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%.

As a preferred embodiment, nonaqueous solvents is organic solvent and/or ionic liquid.

Ionic liquid includes imidazoles, piperidines, pyroles, quaternary amines or one kind in amides ionic liquid or at least Two kinds.

As a preferred embodiment, organic solvent includes propene carbonate (PC), ethylene carbonate (EC), carbonic acid Diethylester (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), N, N- bis- Methylacetamide (DMA), fluorinated ethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), Gamma-butyrolacton (GBL), tetrahydrofuran (THF), 2- methyltetrahydrofurans (2MeTHF), 1,3- dioxolanes (DOL), 4- first Base -1,3- dioxolanes (4MeDOL), dimethoxymethane (DMM), 1,2- diformazans Ethylene Oxide (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl ether (DME), ethylene sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS) or one kind or at least two in sulfurous acid diethyl ester (DES) or crown ether (12-crown-4), preferably ethylene carbonate, carbon The mixed solvent of dimethyl phthalate and methyl ethyl carbonate.

As a preferred embodiment, ionic liquid includes 1- ethyl-3-methylimidazoles-hexafluorophosphate, 1- second Base -3- methylimidazoles-tetrafluoroborate, 1- ethyl-3-methylimidazoles-bis trifluoromethyl sulfimide salt, 1- propyl -3- methyl Imidazoles-hexafluorophosphate, 1- propyl -3- methylimidazoles-tetrafluoroborate, 1- propyl -3- methylimidazoles-bis trifluoromethyl sulphonyl Inferior amine salt, 1- butyl -1- methylimidazoles-hexafluorophosphate, 1- butyl -1- methylimidazoles-tetrafluoroborate, 1- butyl -1- first Base imidazoles-bis trifluoromethyl sulfimide salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyls sulfimide salt, 1- butyl- 1- methylpyrrolidin- bis trifluoromethyls sulfimide salt, N- Methyl-N-propyls pyrrolidines-bis trifluoromethyl sulfimide salt, N- One kind in first, propylpiperdine-bis trifluoromethyl sulfimide salt or N- methyl butyls piperidines-bis trifluoromethyl sulfimide salt Or at least two.

[organic polymer]

The typical but non-limiting mass percentage of organic polymer is, for example, 1%, 2%, 5%, 10%, 15%, 20%th, 25%, 30%, 35%, 40%, 45% or 50%.

As a preferred embodiment, organic polymer includes polyvinyl chloride (PVC), chliorinated polyvinyl chloride, gathers partially Vinyl fluoride (PVDF), polyacrylonitrile (PAN), polyethylene, polypropylene oxide (PPO), polymethyl-benzene e pioic acid methyl ester (PMMA), thermoplastic Property acrylic resin, polyoxyethylene (PEO), vinylidene fluoride-hexafluoropropylene copolymer or one kind in polystyrene or at least two Kind, preferably polyoxyethylene-polymethyl-benzene e pioic acid methyl ester copolymer (PEO-PMMA).

Organogel electrolyte can also not interfere this in addition to above-mentioned electrolyte, nonaqueous solvents and organic polymer Coordinate other ingredients, such as additive in the range of The effect of invention.

[additive]

It is understood that electrolysis additive is not particularly limited, conventional electrolysis solution additive can be used.

The typical but non-limiting mass percentage of additive is, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%th, 7%, 8%, 9% or 10%.

One or more of additives are added in electrolyte can further improve the one or more of sodium base Dual-ion cell Performance is classified from the effect of additive, and additive includes film for additive (such as carbon dioxide, sulfur dioxide, lithium carbonate, carbonic acid Ester, thio organic solvent, halogenated organic film for additive etc.), additives for overcharge protection additive (have oxidation-reduction pair：Ortho position With contraposition dimethoxy substituted benzene, polymerization increase internal resistance, block charging, such as biphenyl, cyclohexyl benzene), stabilizer, improve height Warm nature can additive, conductive additive or flame-retardant additive (organic phosphorus compound, organic fluoric compound, halogenated alkyl phosphoric acid Ester) etc..

Additive can be used alone a kind of above-mentioned additive or be used in a manner of two or more combinations.

Preferably, additive includes organic additives or carbon dioxide, two such as esters, sulfone class, ethers, nitrile, olefines One kind in the inorganic additives such as sulfur oxide, lithium carbonate or at least two；

Preferably, additive includes fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, the third sulphurs of 1,3- Acid lactone, 1,4- butyl sultones, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, sulfurous acid third Enester, dimethyl sulfite, diethyl sulfite, glycol sulfite, methyl chlorocarbonate, dimethyl sulfoxide (DMSO), benzene first Ether, acetamide, diazine, metadiazine, 12- crown ethers -4,18- crown ethers -6,4- fluoroanisoles, fluoro chain ether, difluoro For methyl carbonic acid vinyl acetate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, trifluoroethyl Phosphonic acids, bromo butyrolactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, ethanol amine, carbonization dimethylamine, cyclobutyl Sulfone, 1,3- dioxolanes, acetonitrile, long-chain olefin, alundum (Al2O3), magnesia, barium monoxide, sodium carbonate, calcium carbonate, titanium dioxide One kind in carbon, sulfur dioxide or lithium carbonate or at least two, preferably fluorinated ethylene carbonate.

Using the sodium salt of 1-50wt%, the nonaqueous solvents of 20-85wt%, 1-50wt% organic polymer and 0.5- The organogel electrolyte that the additive of 10wt% obtains has preferable electric conductivity and leads ionic nature, and system machinery is strong It spends and flexible, there is better safety.

According to the second aspect of the invention, a kind of above-mentioned organogel electrolyte is provided in sodium base Dual-ion cell Application.

Sodium base Dual-ion cell is the Dual-ion cell using sodium ion as transmission medium, combines sodium-ion battery and double The advantages of ion battery.

Above-mentioned organogel electrolyte is applied to improve circulating battery stability and longevity in sodium base Dual-ion cell Life, battery remains to keep the performance of good electric conductivity and diversion at room temperature, improves the security performance of battery.

According to the third aspect of the present invention, providing a kind of sodium base double ion including above-mentioned organogel electrolyte has Machine solid state battery.

By using the organogel solid electrolyte of the present invention, have has with above-mentioned sodium base double ion organic solid-state battery The identical advantage of machine gel electrolyte.

As a kind of typical sodium base double ion organic solid-state battery, including cathode, anode, between positive and negative anodes every Film and above-mentioned organogel electrolyte；Cathode is can be with sodium ion alloyed metal (AM), metal alloy or metal composite； Anode includes plus plate current-collecting body and positive electrode, and positive electrode includes active substances in cathode materials, and active substances in cathode materials is It can reversibly be embedded in, the stratified material of deintercalation sodium salt anion.

As shown in Figure 1, the sodium base double ion organic solid-state battery of the present invention includes negative current collector 1, organic in structure Gel electrolyte 2, diaphragm 3, positive electrode material layer 4 and plus plate current-collecting body 5.

[cathode]

The cathode of sodium base double ion organic solid-state battery is can be with sodium ion alloyed metal (AM), metal alloy or metal Compound.

" can be with sodium ion alloyed metal (AM), metal alloy or metal composite " be to refer to be electrolysed with organogel Sodium ion alloyed metal (AM) in matter, can with the alloy of sodium ion alloying in organogel electrolyte or can with it is organic solidifying Sodium ion alloyed metal (AM) compound in glue electrolyte.

As long as metal here can form alloy with sodium, the type of metal is not limited.

Typical but non-limiting metal is tin, copper, iron, nickel, titanium, aluminium, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium etc..

Alloy is the alloy for referring to form the metal of alloy with sodium and formed with other one or more of metals.

Typical but non-limiting alloy is ferro-tin alloy, copper-tin alloy, titanium-aluminium alloy or titanium magnesium alloy etc..

Metal composite is to refer to be combined formed metal with other nonmetallic materials with the metal of sodium formation alloy Based composites.Typical but non-limiting metal composite includes graphene-metal composite, carbon fiber-metal composite With Ceramic-metal composites etc..

Typical but non-limiting metal composite is tin/graphene complex, tin/Polyaniline etc..

Preferably paillon can be made with sodium ion alloyed metal (AM), metal alloy or metal composite by above-mentioned and make With cathode and collector as sodium base double ion organic solid-state battery.

During charging, during embedding sodium, Na⁺Reach negative metal material surface, free electron is obtained on cathode, formed Negative terminal surface is deposited to after Na atoms, inside the diffusion into the surface to negative material of negative material alloy occurs for Na atoms later Change reaction；Conversely, during electric discharge, under high potential, Na atoms lose electronics since chemical property is active in negative terminal surface, are formed Na⁺, into organogel electrolyte, and migrate under electric field action to anode, the Na atoms permeatings inside cathode to cathode Alloy (decomposition of alloy) has occurred in surface for cathode.

Using can with sodium ion alloyed metal (AM), alloy or metal composite as sodium base double ion organic solid-state electricity The negative current collector and negative material (double action for serving as negative electrode active material and negative current collector) in pond, not only act as conduction Also as the active material reacted with sodium ion, a kind of element is omitted in integrated design, saves the body of a component for effect Product and weight reduce the weight and volume of battery, metal material rich reserves, cheap, environmental-friendly, reduction battery manufacture The alloying of cost, metal and sodium/removal alloying reaction process can provide higher specific capacity and energy density.

[anode]

The anode of sodium base double ion organic solid-state battery includes plus plate current-collecting body and positive electrode, and positive electrode includes anode Material activity substance, active substances in cathode materials is can reversibly be embedded in, the stratified material of deintercalation sodium salt anion.

For positive electrode active materials, reversible by anion inserts embedding and deintercalation to obtain high power capacity, during charging, anion It is inserted into the lattice of positive electrode from organogel electrolyte, during electric discharge, anion is deviate from out of positive electrode, passes through intercalation Energy storage is realized in reaction.

Typical but non-limiting stratified material is, for example, graphite-like carbon material, sulfide, nitride, oxide or carbonization Object etc. has the material of layered crystal structure.

It is understood that the plus plate current-collecting body of sodium base double ion organic solid-state anode is conductive metal material, it should Conductive material include but not limited to a kind of metal in aluminium, copper, iron, nickel, titanium, tin, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium or Alloy including at least any one aforementioned metal or the metal composite including at least any one aforementioned metal.

Preferably, plus plate current-collecting body is aluminium foil.

[organogel electrolyte]

The organogel electrolyte of sodium base double ion organic solid-state battery and the organogel of first aspect present invention are electrolysed The description of matter is identical.

Organogel electrolyte includes electrolyte sodium salt, nonaqueous solvents and organic polymer.

Preferably, sodium salt includes sodium hexafluoro phosphate, sodium borohydride, sodium carbonate, sodium bicarbonate, sodium chloride, sodium fluoride, sulfuric acid Sodium, sodium phosphate, sodium nitrate, difluoro oxalate Boratex, sodium pyrophosphate, neopelex, lauryl sodium sulfate, lemon It is sour sodium, kodalk, Boratex, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium metasilicate, wooden Plain sodium sulfonate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, hexafluoroarsenate sodium, sodium tetrafluoroborate, high chlorine Sour sodium, one kind in trifluoromethanesulfonimide sodium or at least two；Preferably sodium hexafluoro phosphate.

Preferably, nonaqueous solvents includes organic solvent and/or ionic liquid.

Preferably, organic solvent includes propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), carbonic acid Dimethyl ester (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), DMAC N,N' dimethyl acetamide (DMA), Fluorinated ethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), gamma-butyrolacton (GBL), four Hydrogen furans (THF), 2- methyltetrahydrofurans (2MeTHF), 1,3- dioxolanes (DOL), 4- methyl-1,3-dioxy pentamethylene (4MeDOL), dimethoxymethane (DMM), 1,2- diformazans Ethylene Oxide (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl ether (DME), ethylene sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS) or sulfurous acid One kind or at least two in diethylester (DES) or crown ether (12-crown-4), preferably ethylene carbonate, dimethyl carbonate and carbon The mixed solvent of sour methyl ethyl ester.

Preferably, organic polymer includes polyvinyl chloride (PVC), chliorinated polyvinyl chloride, Kynoar (PVDF), poly- third Alkene nitrile (PAN), polyethylene, polypropylene oxide (PPO), polymethyl-benzene e pioic acid methyl ester (PMMA), thermoplastic acrylic resin, polyoxy Ethylene (PEO), vinylidene fluoride-hexafluoropropylene copolymer or one kind in polystyrene or at least two, preferably polyoxyethylene- Polymethyl-benzene e pioic acid methyl ester copolymer (PEO-PMMA).

[diaphragm]

It is understood that diaphragm is it is not also specifically limited, using the existing common diaphragm in this field.

In a preferred embodiment, diaphragm includes but not limited to the porous polymer film or inorganic porous to insulate Film.

In a preferred embodiment, diaphragm include but not limited to porous polypropylene film, porous polyethylene film, Porous compound polymer film, non-woven fabrics, all-glass paper or one kind in porous ceramics diaphragm or at least two.

In a preferred embodiment, sodium base double ion organic solid-state battery is further included for the housing of encapsulation or outer Packaging, such as including anode housing 6 and battery cathode housing 7.

Arbitrary outer packing can suitably be selected and unlimited, as long as it is with enough sealing performances.

In addition, sodium base double ion organic solid-state battery shape of the present invention is not limited to button type, it also can be according to core Heart composition design is into the forms such as plate, cylindrical type or laminated type.

Existing lithium ion battery has the problem of shortage of resources, lithium cost recovery is high, lithium battery cost of manufacture is high, organic Electrolyte is volatile, inflammable, explosive and the safety problem brought and existing sodium ion solid state battery have lead ionic nature and Electric conductivity cannot have both, and there are safety problems under high temperature.

The operation principle of the typical sodium base double ion organic solid-state battery is：In charging process, in gel electrolyte Anion transport to anode and embedded positive electrode active materials in, sodium ion is migrated to cathode, and alloy phase is formed with negative metal； Anion is deviate to return in gel electrolyte from positive electrode in discharge process, and the alloy that sodium ion is formed from cathode is mutually deviate from It returns in gel electrolyte, so as to fulfill entire charge and discharge process.In this process, electrolyte is all by sodium salt instead of tradition Lithium salts, solve the problems, such as that lithium resource reserves are limited, reduce cost, alleviate influence of the battery to environment.

The typical sodium base double ion organic solid-state battery is with can be with sodium ion alloyed metal (AM), metal alloy or gold Belong to compound as negative material and collector, can reversibly be embedded in, the stratified material of deintercalation sodium salt anion is being as just Pole material activity substance, to contain the organogel of sodium salt as electrolyte, the alloying by sodium ion and metal foil is anti- Should and insertion of the sodium salt anion on positive electrode, abjection realize the storage of energy.Sodium base double ion organic solid-state electricity Pond has advantage with organogel electrolyte, can alleviate the volume expansion that is brought due to alloying and caused by pole piece dusting Problem so as to improve the cyclical stability of battery, realizes the long lifetime of battery；Positive and negative pole material is simple, be easy to get, environmental protection, Safety；And organic electrolyte has good flexibility, has widened the application field of battery；Sodium base double ion organic solid-state battery It remains to keep the performance of good electric conductivity and diversion at room temperature, so as to reduce the temperature in use of battery, improves electricity The security performance in pond.

In a preferred embodiment, cathode for tin, copper, iron, nickel, titanium, aluminium, zinc, manganese, lead, antimony, cadmium, gold, bismuth or The metal of any one in germanium；Or, cathode be including at least tin, copper, iron, nickel, titanium, aluminium, zinc, manganese, lead, antimony, cadmium, gold, bismuth or The alloy of any one in germanium；Or, cathode be including at least tin, copper, iron, nickel, titanium, aluminium, zinc, manganese, lead, antimony, cadmium, gold, bismuth or The metal composite of any one in germanium.

Preferably, cathode is tin, tin alloy or stanniferous compound.

In a preferred embodiment, active substances in cathode materials includes graphite-like carbon material, sulfide, nitridation Object, one kind of oxide or carbide material or at least two.

Preferably, graphite-like carbon material includes carbonaceous mesophase spherules graphite, native graphite, expanded graphite, vitreous carbon, carbon carbon Composite material, carbon fiber, hard carbon, porous charcoal, highly oriented graphite, carbon black, carbon nanotube or one kind in graphene or at least two Kind, preferably expanded graphite.

Preferably, sulfide includes molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, ferrous disulfide, vulcanization Asia One kind in iron, nickel sulfide, zinc sulphide, cobalt sulfide or manganese sulfide or at least two.

Preferably, nitride includes one or both of hexagonal boron nitride or carbon doping hexagonal boron nitride.

Preferably, oxide includes molybdenum trioxide, tungstic acid, vanadic anhydride, vanadium dioxide, titanium dioxide, oxidation One kind in zinc, copper oxide, nickel oxide or manganese oxide or at least two.

In a preferred embodiment, positive electrode includes the active substances in cathode materials of 60-90wt%, 5- The conductive agent of 30wt% and the binding agent of 5-10wt%.

It is understood that conductive agent and binding agent in positive electrode are it is not also specifically limited, that this field can be used is general Lead to common conductive agent and binding agent.

In a preferred embodiment, conductive agent for conductive black (acetylene black, Super P, Super S, 350G or Ketjen black), conductive carbon ball, electrically conductive graphite, carbon nanotube, carbon fiber or one kind in graphene or at least two.

In a preferred embodiment, binding agent is Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl One kind or at least two in cellulose, SBR rubber, polyolefins (polybutadiene, polyvinyl chloride, polyisoprene etc.).

Wherein mass percent is using positive electrode as calculating benchmark.

The typical but non-limiting mass percent of active substances in cathode materials is for example 60%, 70%, 75%, 80%, 85% or 90%.

The typical but non-limiting mass percent of conductive agent is for example 5%, 10%, 15%, 20%, 25% or 30%.

The typical but non-limiting mass percent of binding agent is for example 5%, 6%, 7%, 8%, 9% or 10%.

The positive electrode obtained using the active substances in cathode materials of specific percentage composition, conductive agent and binding agent is comprehensive Can be good, effect of the positive electrode in sodium base double ion organic solid-state battery can be played well.

According to the fourth aspect of the present invention, a kind of preparation side of above-mentioned sodium base double ion organic solid-state battery is provided Method assembles cathode, organogel electrolyte, diaphragm and anode, obtains sodium base double ion organic solid-state battery.

It is understood that the assembling mode of cathode, organogel electrolyte, diaphragm and anode is not particularly limited, Conventional assembling mode may be used to carry out.

The preparation method of sodium base double ion organic solid-state battery by above-mentioned cathode, organogel electrolyte, diaphragm, anode into Row assembling, it is simple production process, at low cost.

As a preferred embodiment, the preparation method of sodium base double ion organic solid-state battery, includes the following steps：

Preferably, typical solvent includes water or N-Methyl pyrrolidone in step d).

Preferably, it is specifically included during assembling：In the glove box of inert gas shielding, by the above-mentioned negative pole currect collecting prepared Body, diaphragm, anode Close stack successively, add in pre-arranged gel electrolyte, treat gel electrolyte in battery case It is sufficiently spread out, stacks gradually gasket, shrapnel at this time, above-mentioned stacking portion is encapsulated into button cell housing, complete battery assembling.

It should be noted that although above-mentioned steps are that the operation of preparation method of the present invention is described with particular order, This, which does not require that or implies, to perform these operations according to the particular order.Step a), preparation b), c) and d) can be with Simultaneously or arbitrary priority performs.

The preparation method of the sodium base double ion organic solid-state battery and aforementioned sodium base double ion organic solid-state battery are to be based on Same inventive concept, the sodium base double ion organic solid-state obtained using the preparation method of the sodium base double ion organic solid-state battery Institute of the battery with aforementioned sodium base double ion organic solid-state battery is effective, and details are not described herein.

It is further illustrated the present invention below by specific embodiment and comparative example, it should be understood, however, that, these implementations Example, which is only used for being described in more detail, to be used, and is not to be construed as limiting the present invention in any form.

Embodiment 1

A kind of sodium base double ion organic solid-state battery, including cathode, diaphragm, organogel electrolyte and anode.

Prepare cathode：Using collector and the integrated tinfoil paper of cathode, respectively successively with deionized water, acetone, ethyl alcohol pair Tinfoil paper be cleaned by ultrasonic 3-5 minutes, and the disk of diameter 12mm is cut into after to be dried, spare as cathode；

Prepare diaphragm：Glass fiber membrane is cut into spare as diaphragm after the disk of diameter 16mm.

Prepare organic gel electrolyte：It weighs 3g sodium hexafluoro phosphates and is added to 5mL ethylene carbonates, dimethyl carbonate and carbon The in the mixed solvent of sour methyl ethyl ester, stirs to sodium hexafluoro phosphate and is completely dissolved, and then adds in the fluoro carbonic acid that mass fraction is 5% As additive, the organic polymer matrix that mass fraction 20% is added in after stirring is uniformly mixed vinyl acetate, as Organogel electrolyte is spare.

Prepare anode：0.8g expanded graphites, 0.1g carbon blacks, 0.1g Kynoar are added to 2mL N- crassitudes In ketone solution, it is fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface (plus plate current-collecting body) and vacuum It is dry.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.

Battery assembles：In the glove box of inert gas shielding, by the above-mentioned negative current collector prepared, diaphragm, battery Anode Close stack successively, adds in a few prepared moulding dose of classes of drop into electrolyte first, and stirring treats that it is completely dissolved in electrolysis Liquid, the electrolyte containing moulding dose of class is added dropwise at this time makes diaphragm complete wetting, then stacks anode, liquid to be electrolysed is slowly plasticized into Gel stacks gradually gasket, shrapnel at this time, and above-mentioned stacking portion is encapsulated into button cell housing, completes battery assembling.

Embodiment 2-20

The sodium base double ion organic solid-state battery of embodiment 2-20 uses the tinfoil paper cathode material identical in embodiment 1 Material, fibreglass diaphragm, identical electrolytic salt, the electrolyte of same concentrations and graphite positive electrode, the difference is that adding in Organic polymer.

The chemical property of embodiment 1 and embodiment 2-20 is tested, including cycle-index, capacity retention ratio and library Human relations efficiency.Test method is as follows：

Cycle charge-discharge：Cycle charge-discharge carries out in the blue electric circulating battery test systems of CT2001C-001, with 100mA/ The normal capacity of electrode, specific capacity=electric current * times/sample quality of material, the energy density of material are tested in the charge and discharge of g multiplying powers The platform voltage of the specific capacity * batteries of=material, depending on the needs of experiment, circulation step includes the condition of charge and discharge：It stands 60s- constant-current discharges-standing 60s- constant-current charges.

Rate charge-discharge：Equally carried out in blue electric circulating battery test system, with different multiplying powers (current density) into Row charge and discharge carrys out the high rate performance of test material, and the condition of charge and discharge is depending on the needs of experiment, circulation step and cycle charge-discharge It is identical.

Embodiment 1 and the performance parameter of embodiment 2-20 such as table 1.

The performance data table of 1 embodiment 2-20 of table

From table 1 it follows that the present invention is lived using the tinfoil paper that sodium ion can be made to form alloy as integrated cathode Property material and collector, be capable of it is reversible insert embedding-deintercalation expanded graphite as a positive electrode active material sodium double ion solid-state electricity Solution electrolyte cell has higher efficiency for charge-discharge, cyclical stability, and solve liquid electrolyte because volatile, inflammable, easy Safety issue caused by quick-fried.

Embodiment 2-20 is compared with embodiment 1, and the matrix of added organic polymer is different in electrolyte.It can from table 1 To find out, chemical property can be influenced using different organic polymer matrix, different organic polymer matrix have different officials It can roll into a ball, different connection modes, the inevitable viscosity of gel electrolyte formed, electronic conductivity, ion conduction property are different, So as to influence the chemical property of battery.It is protected using the cycle-index of 1 battery of embodiment of PEO-PMMA organic polymers, capacity Holdup and coulombic efficiency performance are best.

Embodiment 21-29

The sodium base double ion organic solid-state battery of embodiment 21-29 uses the tinfoil paper cathode material identical in embodiment 1 Material, fibreglass diaphragm, identical electrolytic salt, the electrolyte of same concentrations, identical organic polymer matrix (PEO：PMMA =1：1/ mass ratio) and graphite positive electrode, the difference is that the content of the organic polymer added in.

The chemical property of embodiment 21-29 is tested, test method is the same as embodiment 1.

The performance parameter of embodiment 21-29 such as table 2.

The performance data table of 2 embodiment 21-29 of table

Compared with Example 1, the additive amount of organic polymer matrix is different in electrolyte, can from table 2 by embodiment 21-29 To find out, polymeric matrix addition is probed into from 5%-50% in embodiment 21-29, different additions to coagulate The accumulation of molecule generates larger difference in glue electrolyte, so as to have large effect to the transmission channel of ion.It is real compared to relatively It is best to apply battery performance obtained by example 1 20% additive amount.

Embodiment 30-35

The sodium base double ion organic solid-state battery of embodiment 30-35 uses the tinfoil paper cathode material identical in embodiment 1 Material, fibreglass diaphragm, identical electrolytic salt, the electrolyte of same concentrations, identical organic polymer matrix (addition 20wt%) and graphite positive electrode, the ratio of the two kinds of organic polymers added in unlike.

The chemical property of embodiment 30-35 is tested, test method is the same as embodiment 1.

The performance parameter of embodiment 30-35 such as table 3.

The performance data table of 3 embodiment 30-35 of table

Embodiment 30-35 compared with Example 1, under the premise of polymeric matrix addition is identical in electrolyte is ensured, The adding proportion of two kinds of polymer is had adjusted, so as to obtain the electrochemistry based on different polymer proportioning solid electrolyte battery It can data.From table 3 it is observed that two kinds of polymer presses 1：The sodium double ion solid state battery that 1 ratio is added Chemical property is more preferable.

Comparative example 1

A kind of solid-state sodium-ion battery, respectively with Na- β-Al₂O₃For solid electrolyte, using graphite as cathode, with vanadium phosphate Sodium is anode, assembles sodium ion solid state battery.Wherein, the preparation of electrolyte sheet is synthesized first using sol-gel method NaAl₅O₈And LiAl₅O₈, the two progress ball milling is then obtained into Na according to certain stoichiometric ratio_1.67Al_10.67Li_0.33O₁₇, β-Al are obtained using 1600 DEG C of sintering₂O₃Potsherd.

After after tested, circulating battery number is 100；Capacity retention ratio is 90%；Coulombic efficiency is 95%.

Comparative example 2

A kind of sodium base Dual-ion cell, including cathode, diaphragm, electrolyte and anode.Wherein prepare electrolyte：It weighs 0.84g sodium hexafluoro phosphates are added to the in the mixed solvent (volume ratio of 5mL ethylene carbonates, dimethyl carbonate and methyl ethyl carbonate It is 1:1:1) it, stirs to sodium hexafluoro phosphate and is completely dissolved, it is spare as electrolyte after stirring.Positive electrode is expansion Graphite, negative material are tin, other are same as Example 1.

After after tested, circulating battery number is 400；Capacity retention ratio is 94%；Coulombic efficiency is 95%.

For comparative example 1 compared with the embodiment of the present invention, comparative example 1 uses the preparation work of traditional inorganic solid electrolyte Skill, although fast-ionic conductor so that leading ionic nature obtains larger improvement, its interface problem cause its coulombic efficiency compared with Low, then its capacity retention ratio is than relatively low, and the preparation method of traditional solid electrolyte is complex, cumbersome, so as to increase The production cost of battery is added.

For comparative example 2 compared with the embodiment of the present invention, comparative example 2 is a kind of sodium base Dual-ion cell, and electrolyte is carbonic acid The liquid mixed solvent of lipid has the safety problems such as volatile, inflammable, explosive common to conventional organic solution liquid, and real The gel electrolyte in example is applied, under the premise of electron-transport, ion conduction is ensured, still there is preferable chemical property, and And solves the safety problem brought due to electrolyte is volatile, inflammable.

Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that it wraps in the following claims Include all such changes and modifications belonged in the scope of the invention.

Claims

1. a kind of organogel electrolyte, which is characterized in that including electrolyte sodium salt, nonaqueous solvents, organic polymer and appoint The additive of choosing.

2. organogel electrolyte described in accordance with the claim 1, which is characterized in that the following component including mass percent： Sodium salt 1-50%, nonaqueous solvents 20-85%, organic polymer 1-50% and additive 0.5-10%；

Preferably, electrolyte sodium salt includes sodium hexafluoro phosphate, sodium borohydride, sodium carbonate, sodium bicarbonate, sodium chloride, sodium fluoride, sulphur Sour sodium, sodium phosphate, sodium nitrate, difluoro oxalate Boratex, sodium pyrophosphate, neopelex, lauryl sodium sulfate, lemon Lemon acid sodium, kodalk, Boratex, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, sodium metasilicate, wood Quality sodium sulfonate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, hexafluoroarsenate sodium, sodium tetrafluoroborate, height Sodium chlorate or one kind in trifluoromethanesulfonimide sodium or at least two；Preferably sodium hexafluoro phosphate；

Preferably, nonaqueous solvents is organic solvent and/or ionic liquid；

Preferably, organic solvent includes esters, sulfone class, ethers, nitrile or one kind in olefines organic solvent or at least two； And/or

Ionic liquid includes imidazoles, piperidines, pyroles, quaternary amines or one kind in amides ionic liquid or at least two Kind；

Preferably, organic solvent includes propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate Ester, methyl formate, methyl acetate, DMAC N,N' dimethyl acetamide, fluorinated ethylene carbonate, methyl propionate, ethyl propionate, acetic acid second Ester, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- dioxolanes, 4- methyl-1,3-dioxies pentamethylene, two Methoxy methane, 1,2- diformazans Ethylene Oxide, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, sulfurous acid third One kind in enester, dimethyl sulfite or sulfurous acid diethyl ester or crown ether or at least two, preferably ethylene carbonate, carbonic acid The mixed solvent of dimethyl ester and methyl ethyl carbonate；

Preferably, ionic liquid includes 1- ethyl-3-methylimidazoles-hexafluorophosphate, 1- ethyl-3-methylimidazoles-tetrafluoro boron Hydrochlorate, 1- ethyl-3-methylimidazoles-bis trifluoromethyl sulfimide salt, 1- propyl -3- methylimidazoles-hexafluorophosphate, 1- third Base -3- methylimidazoles-tetrafluoroborate, 1- propyl -3- methylimidazoles-bis trifluoromethyl sulfimide salt, 1- butyl -1- methyl Imidazoles-hexafluorophosphate, 1- butyl -1- methylimidazoles-tetrafluoroborate, 1- butyl -1- methylimidazoles-bis trifluoromethyl sulphonyl The double fluoroforms of inferior amine salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyls sulfimide salt, 1- butyl -1- methylpyrrolidin- Base sulfimide salt, N- Methyl-N-propyls pyrrolidines-bis trifluoromethyl sulfimide salt, N- first, propylpiperdine-bis- fluoroforms One kind or at least two in base sulfimide salt or N- methyl butyls piperidines-bis trifluoromethyl sulfimide salt.

3. according to the organogel electrolyte described in claims 1 or 2, which is characterized in that organic polymer include polyvinyl chloride, Chliorinated polyvinyl chloride, Kynoar, polyacrylonitrile, polyethylene, polypropylene oxide, polymethyl-benzene e pioic acid methyl ester, thermoplasticity third One kind in olefin(e) acid resin, polyoxyethylene, vinylidene fluoride-hexafluoropropylene copolymer or polystyrene or at least two；Preferably Polyoxyethylene-polymethyl-benzene e pioic acid methyl ester copolymer；

Preferably, additive include film for additive, additives for overcharge protection additive, stabilizer, improve high temperature performance additive, One kind in conductive additive or flame-retardant additive or at least two；

Preferably, additive includes fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1, in 3-N-morpholinopropanesulfonic acid Ester, 1,4- butyl sultones, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, propylene sulfite, Dimethyl sulfite, diethyl sulfite, glycol sulfite, methyl chlorocarbonate, dimethyl sulfoxide (DMSO), methyl phenyl ethers anisole, second Amide, diazine, metadiazine, crown ether 12-crown-4, crown ether 18- crown-s 6,4- fluoroanisoles, fluoro chain ether, two fluoro Methyl carbonic acid vinyl acetate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, trifluoroethyl phosphine Acid, bromo butyrolactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, ethanol amine, carbonization dimethylamine, cyclobutyl sulfone, 1,3- dioxolanes, acetonitrile, long-chain olefin, alundum (Al2O3), magnesia, barium monoxide, sodium carbonate, calcium carbonate, carbon dioxide, One kind in sulfur dioxide or lithium carbonate or at least two, preferably fluorinated ethylene carbonate.

4. application of the claim 1-3 any one of them organogel electrolyte in sodium base Dual-ion cell.

5. include the sodium base double ion organic solid-state battery of claim 1-3 any one of them organogel electrolyte.

6. according to the sodium base double ion organic solid-state battery described in claim 5, which is characterized in that including cathode, anode, between Diaphragm and the organogel electrolyte between positive and negative anodes；

The anode includes plus plate current-collecting body and positive electrode, and positive electrode includes active substances in cathode materials, and positive electrode is lived Property substance for can reversibly be embedded in, the stratified material of deintercalation sodium salt anion.

7. according to the sodium base double ion organic solid-state battery described in claim 6, which is characterized in that the cathode for tin, copper, The metal of any one in iron, nickel, titanium, aluminium, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium；Or,

The cathode is including at least any one in tin, copper, iron, nickel, titanium, aluminium, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium Alloy；Or,

The cathode is including at least any one in tin, copper, iron, nickel, titanium, aluminium, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium Metal composite；

Preferably, the cathode is tin, tin alloy or stanniferous compound.

8. according to the sodium base double ion organic solid-state battery described in claim 6, which is characterized in that active substances in cathode materials packet Include one kind in graphite-like carbon material, sulfide, nitride, oxide or carbide material or at least two；

Preferably, it is compound to include carbonaceous mesophase spherules graphite, native graphite, expanded graphite, vitreous carbon, carbon carbon for graphite-like carbon material Material, carbon fiber, hard carbon, porous charcoal, highly oriented graphite, carbon black, carbon nanotube or one kind in graphene or at least two；

Preferably, sulfide includes molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, ferrous disulfide, ferrous sulfide, sulphur Change nickel, zinc sulphide, cobalt sulfide or one kind in manganese sulfide or at least two；

Preferably, oxide includes molybdenum trioxide, tungstic acid, vanadic anhydride, vanadium dioxide, titanium dioxide, zinc oxide, oxygen Change copper, nickel oxide or one kind in manganese oxide or at least two；

Preferably, carbide includes one kind or at least two in titanium carbide, ramet, molybdenum carbide or silicon carbide；

Preferably, the active substances in cathode materials of positive electrode including 60-90wt%, 5-30wt% conductive agent and 5-10wt% Binding agent；

Preferably, conductive agent in conductive black, conductive carbon ball, electrically conductive graphite, carbon nanotube, carbon fiber or graphene one Kind or at least two；

Preferably, binding agent is selected from Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, SBR rubber or poly- One kind in olefines binding agent or at least two；

Preferably, plus plate current-collecting body is any one in aluminium, copper, iron, nickel, titanium, tin, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium Metal；Or, plus plate current-collecting body is including at least arbitrary in aluminium, copper, iron, nickel, titanium, tin, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium A kind of alloy；Or, plus plate current-collecting body is including at least aluminium, copper, iron, nickel, titanium, tin, zinc, manganese, lead, antimony, cadmium, gold, bismuth or germanium In the metal composite of any one；Preferably, plus plate current-collecting body is aluminium foil.

9. a kind of preparation method of claim 5-8 any one of them sodium base double ion organic solid-state battery, which is characterized in that Cathode, organogel electrolyte, diaphragm and anode are assembled, obtain sodium base double ion organic solid-state battery.

10. according to the preparation method of the sodium base double ion organic solid-state battery described in claim 9, which is characterized in that including with Lower step：

B) organic gel electrolyte is prepared：Sodium salt electrolyte is dissolved in nonaqueous solvents, organic polymer is added after being sufficiently mixed Object obtains organogel electrolyte；

D) anode is prepared：Active substances in cathode materials, conductive agent and binding agent and solvent are mixed and made into slurry；Again by anode material Slurry material is evenly applied to plus plate current-collecting body surface, and cut-parts after drying obtain the anode of required size；

The diaphragm and step d) that organogel electrolyte, the step c) that cathode, the step b) that step a) is obtained are obtained are obtained Obtained anode is assembled, and obtains sodium base double ion organic solid-state battery.