CN107171018B - A kind of semisolid lithium slurry battery - Google Patents

A kind of semisolid lithium slurry battery Download PDF

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Publication number
CN107171018B
CN107171018B CN201610128524.8A CN201610128524A CN107171018B CN 107171018 B CN107171018 B CN 107171018B CN 201610128524 A CN201610128524 A CN 201610128524A CN 107171018 B CN107171018 B CN 107171018B
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lithium
anode
porous
battery
conductive
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CN107171018A (en
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陈永翀
张晓虎
张艳萍
张萍
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BEIJING HAWAGA POWER STORAGE TECHNOLOGY Co Ltd
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BEIJING HAWAGA POWER STORAGE TECHNOLOGY Co Ltd
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Priority to CN201610128524.8A priority Critical patent/CN107171018B/en
Priority claimed from US16/082,838 external-priority patent/US10868337B2/en
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention provides a kind of semisolid lithium slurry battery, inside the anode comprising can rheology electrocondution slurry, cathode be metal lithium sheet or it is other contain lithium cathode sheet, and be provided between positive and negative anodes the separate cavities that a spacing is greater than zero, be full of electrolyte in separate cavities.Can rheology electrocondution slurry can fall off or loosen to avoid electrode material caused by cycle life attenuation problem;Separate cavities full of electrolyte avoid the close contact of positive/negative plate and separation layer, and by the electrolyte in periodic replacement battery, can be effectively reduced battery polarization, extend battery, improve battery security.

Description

A kind of semisolid lithium slurry battery
Technical field
The invention belongs to chemomotive force battery technologies, and in particular to a kind of semisolid lithium slurry battery.
Background technique
Lithium ion battery is the novel high-energy battery using lithium intercalation compound as positive and negative pole material, with lead-acid battery, ni-mh Battery is compared to having the advantages that high specific energy, voltage height, small, good cycle and the service life length of self discharge etc. are a series of, increasingly It is concerned by people.In recent years, lithium ion battery technology achieves fast development, has started to be applied in electric car.
Power source of the lithium ion battery as electric car, at present there is also capacity attenuation is too fast and security hidden trouble, Main cause is: 1) some side reactions that inside lithium ion cell generates consume electrolyte, cause to participate in cell reaction in battery Electrolyte and recyclable lithium ion it is fewer and fewer, battery polarization increase, circulation volume decline;2) automobile bumpiness When, the electrode material being bonded on a current collector falls off or loosens, and amount of activated particle loses conductive contact, influences the battery longevity Life;3) active material particle or conductive agent are embedded in separation layer micropore battery during the work time, are blocked separation layer, are made in battery Resistance increases, capacity attenuation;4) it is easy to produce " Li dendrite " in negative side during quickly charging battery, when positive and negative anodes and separation layer When close contact, " Li dendrite ", which can pierce through separation layer, leads to internal short-circuit of battery, and inside battery generates amount of heat, sends out when serious Raw explosion on fire.
Summary of the invention
For the problem present on, the present invention provides a kind of semisolid lithium slurry battery, includes inside the anode Can rheology electrocondution slurry, cathode be metal lithium sheet or it is other contain lithium cathode sheet, and a spacing is provided between positive and negative anodes Separate cavities greater than zero, separate cavities are interior to be full of electrolyte.Can rheology electrocondution slurry can be fallen off to avoid electrode material or Cycle life attenuation problem caused by loosening;Separate cavities full of electrolyte avoid positive/negative plate and the close of separation layer connects Touching, and by the electrolyte in periodic replacement battery, it can be effectively reduced battery polarization, extend battery, improve Battery security.
It is as follows that the present invention provides technical solution:
A kind of semisolid lithium slurry battery, including battery core, the battery core include several alternately place it is sandwich it is compound just Pole piece and contain lithium cathode sheet, sandwich anode composite piece and containing between lithium cathode sheet be equipped with height be 0.1~1mm separate cavities, institute It states in separate cavities full of electrolyte;The sandwich anode composite piece includes porous afflux anode layer and electrocondution slurry, porous afflux Anode layer is made of the single or double of porous anode collector coating porous anode material layer, two porous afflux anodes The electrocondution slurry of 0~5mm thickness is filled between layer, part or all of electrocondution slurry penetrates into the hole of porous afflux anode layer It is interior, form sandwich anode composite piece;The sandwich anode composite piece is surrounded by insulated enclosure frame, and the insulated enclosure frame is in " returning " shape, and with porous afflux anode layer edge fixing seal, prevent electrocondution slurry from revealing from sandwich four side of anode composite piece;Institute Stating containing lithium cathode sheet includes negative current collector, and the single or double of negative current collector is equipped with a thickness of the negative containing lithium of 0.02~2mm Pole material layer, the layer containing lithium titanate cathode material are lithium metal, high lithium alloy or rich lithium inorganic non-metallic material.
The porous afflux anode layer is with a thickness of 0.05~2.5mm, and porosity is 30%~90%, average pore size scope 0.001 μm~10 μm;Electrolyte and/or polymer dielectric, the polymerization are full of in the hole of the porous afflux anode layer Object electrolyte is that the gel polymer electrolyte of polymeric matrix, liquid organic plasticizers and the compound composition of lithium salts three parts is compound Material.The porous afflux anode layer two sides are equipped with the separation layer for the electronic isolation being in close contact, and the thickness of the separation layer Degree is less than or equal to 2/3rds of separate cavities thickness.
Alternatively, the porous afflux anode layer two sides do not set separation layer, especially as height >=0.5mm of separate cavities, Sandwich anode composite piece be isolated intracavitary electrolyte containing lithium cathode sheet and be isolated, it is difficult to be in contact short circuit.
The separation layer is polyethylene, polypropylene, Kynoar or the nonconducting porous polymer material of other electronics; Alternatively, separation layer is that glass fibre non-woven, non-woven fabrics of synthetic fiber, ceramic fiber paper or other electronics are nonconducting inorganic non- The composite porous material of metal material and organic polymer;Alternatively, the material of separation layer uses the nonconducting polymer matrix of electronics The gel polymer electrolyte composite material of body, liquid organic plasticizers and the compound composition of lithium salts three parts.Further, described Leaching in the hole of the composite porous material of the nonconducting porous polymer material of electronics, inorganic non-metallic material and organic polymer Stain has the electrolyte or polymeric colloid material of ionic conduction.The main function of separation layer is that positive and negative anodes is avoided directly to contact and lead Cause internal short-circuit of battery.
The sandwich anode composite piece is equipped with positive pole ear, and two of the positive pole ear and sandwich anode composite piece are porous Plus plate current-collecting body electrical connection, and extend from sandwich anode composite piece, all positive pole ears are electrically connected and extend electricity in battery core Core;Described to be equipped with negative lug containing lithium cathode sheet, the negative lug is electrically connected with negative current collector, all cathode poles in battery core Ear is electrically connected and extends battery core.
The porous afflux anode layer of the sandwich anode composite piece is coated just by the one or both sides of porous anode collector Pole material layer is constituted, and the porous anode collector is the electronic conduction with through-hole structure with a thickness of 0.01~1000 μm Layer, through-hole porosity are 10%~90%, pore diameter range 0.05nm~2mm.The porous anode collector is conductive filler With the porous mixture of binder, wherein conductive filler is carbon black, carbon nanotube, carbon fiber, graphene, titanium valve, aluminium powder, silver Powder, alloy aluminium powder, stainless steel powder or silver powder, rich lithium silicon powder, lithium alloys powder metalloid alloy conductive particle, or carbon containing lithium One or more of material, binder are polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), gather to benzene Dicarboxylic acid esters, polyamide, polyimides, polyethers nitrile, polymethyl acrylate, Kynoar, polyurethane, polyacrylonitrile, butylbenzene The mass fraction of one or more of rubber, sodium carboxymethylcellulose, improved polyalkene, conductive filler is not less than 70%;Or Person, the porous anode collector are the metal conducting layer with porous structure, and metal conducting layer is metal mesh, wire or table Metal wire knitted of the face with conductive carbon material coating forms, and mesh is rectangular, diamond shape, rectangle or polygon etc.;Alternatively, institute Stating metal conducting layer is the porous foam metal layer with porous structure, or is expanded metal or metal foil through mechanical stamping Or chemical attack forms, the material of metal conducting layer is aluminium, alloy aluminum, stainless steel, silver, tin or titanium, preferably aluminium;Alternatively, institute Stating porous anode collector is conductive carbon fibre conductive fabric, wire and organic fiber silk hybrid conductive cloth, surface coating conduction Carbon material coating or the porous organic material for being coated with metallic film, the porous organic material include natural linen-cotton, terylene, virtue Synthetic fibre, nylon, polypropylene fibre, polyethylene, polytetrafluoroethylene (PTFE) and other electrolyte resistances can good organic matter, the wire and plated The material of metal-plated film is aluminium, alloy aluminum, stainless steel or silver, preferably aluminium;Alternatively, the porous anode collector is above-mentioned Two or more any composed composite current collectors in several collectors.
The porous anode material layer is positive electrode active materials: conductive agent: binder is 59~98%:1 according to mass ratio ~40%:1~10% is uniformly mixed, and is coated in the dry drying tabletting of porous anode collection liquid surface.
Further, the positive electrode active materials are LiFePO4, lithium manganese phosphate, lithium metasilicate, ferric metasilicate lithium, sulfate chemical combination Object, sulphur carbon complex, sulphur simple substance, titanium sulphur compound, molybdenum sulfur compound, iron sulphur compound, doped lithium manganese oxide, lithium cobalt oxidation Object, Li-Ti oxide, lithium-barium oxide, Li, Ni, Mn oxide, lithium nickel cobalt oxides, lithium nickel cobalt aluminum oxide, lithium nickel alumina Object, lithium nickel cobalt manganese oxide, lithium iron Ni, Mn oxide and it is other can one of lithium intercalation compound or a variety of.
The electrocondution slurry includes electrolyte and the positive conductive particle that can be flowed in the electrolytic solution, wherein anode The mass ratio of conductive particle and electrocondution slurry is 10%~90%, and average grain diameter is 0.5 μm~500 μm;The positive conductive Grain is the conductive agents such as carbon black, Ketjen black, graphene, carbon nanotube, carbon fiber, amorphous carbon and all kinds of metallic conduction particles One or more of compound, compound mode includes surface cladding, bonding or mechanical mixture;Alternatively, the positive conductive particle is The compound or mixture of positive electrode active materials and above-mentioned all kinds of conductive agents, wherein the quality of positive electrode active materials and conductive agent Than being 0~98%, compound or mixed mode includes surface cladding, bonding or mechanical mixture.
In the present invention, positive electrode active materials particle fraction contained by the electrocondution slurry is more than or equal to zero.Electrocondution slurry is more An elastic conduction network is formed between the afflux anode layer of hole, when battery is by concussion impact, is bonded in porous anode afflux For positive electrode material layer on body regardless of whether falling off or loosening, active material particle keeps conduction to connect with electrocondution slurry always Touching reduces battery capacity and service life without losing conductive contact as conventional batteries.
Described containing lithium cathode sheet includes negative current collector, and the one or both sides of negative current collector are equipped with a thickness of 0.02~ The layer containing lithium titanate cathode material of 2mm, the layer containing lithium titanate cathode material are lithium metal, high lithium alloy and other rich lithium materials etc., are born Pole collector and layer containing lithium titanate cathode material directly apply pressing by outside force, or by conductive adhesive, or logical in edge position Cross insulating trip carry out bonding or hot pressing fix.
The negative current collector is the electron conducting layer with a thickness of 0.01~1000 μm, and the negative current collector is located at cathode In reaction chamber, and the conducting position of negative current collector does not contact directly with unipolarity separation layer;The negative current collector is conduction Metal plate, metal foil, metal mesh or conductive fabric, preferably metal mesh;The material of the conductive metal sheet, metal foil or metal mesh Including copper, stainless steel, nickel, titanium, silver, tin, tin-coated copper, nickel-clad copper, silver-plated copper, preferably copper;Further, the metal plate, The surface of metal foil or metal mesh is coated with conductive carbon material coating or the composite metal lithium by way of pressing or being electroplated;It is described Conductive fabric be electric conduction of carbon fiber cloth, wire and organic fiber silk hybrid conductive cloth or surface coat conductive carbon material coating or It is coated with the porous organic material of metallic film, the porous organic material includes natural linen-cotton, terylene, aramid fiber, nylon, poly- third Alkene, polyethylene, polytetrafluoroethylene (PTFE) and other electrolyte resistances can good organic matters.
Since lithium metal has the high theoretical specific capacity of 3860mAh/g, while independent lithium source can be provided, therefore can make For the cathode of lithium battery, battery energy density and power density are improved.Therefore, the present invention in negative electrode material using lithium metal, High lithium alloy or other rich lithium inorganic non-metallic materials.
In the present invention, the sandwich anode composite piece of the semisolid lithium slurry battery and containing being equipped with isolation between lithium cathode sheet Chamber, separate cavities are full of electrolyte, and electrolyte has preferable ionic conduction characteristic and electronic isolation characteristic, in battery use process In, the electrolyte shaken in separate cavities can destroy the bridge joint of conductive particle formation, avoid inside battery that short circuit occurs, and improve dynamic The safety in utilization of power battery.
Further, semisolid lithium slurry battery of the present invention further includes positive cover board and negative cover, and the anode cover board is set There is the seal groove for accommodating positive pole ear, positive pole ear extends out of seal groove to be connect with external conductive;The negative cover is set There is the seal groove for accommodating negative lug, negative lug is extended out of seal groove to be connect with external conductive.
Further, semisolid lithium slurry battery of the present invention further includes insulation cover plate, positioned at the two sides of battery core.
Further, semisolid lithium slurry battery of the present invention further includes two electrolyte cover boards, and the electrolyte cover board is fixed In the two sides of battery core separate cavities electrolyte inside circulation, electrolyte cover board is equipped with injecting electrolytic solution mouth, in the electrolyte cover board Equipped with liquid storage chamber, it is full of electrolyte in liquid storage chamber, the liquid storage chamber is connected to the separate cavities of battery core.
Electrolyte, each section electricity are full of in the separate cavities of the semisolid lithium slurry battery, the liquid storage chamber of electrolyte cover board Solution liquid is in connected state, therefore, can effectively improve the consistency of each battery unit electrolyte of battery core.
The electrolyte cover board is additionally provided with heating device, and the heating device is resistance wire, PCT heating sheet and silicon rubber The electrolyte temperature entered in battery core can be heated to 25~60 DEG C by glue heating plate etc.;Battery can be improved in high-temperature electrolyte Ionic conductivity reduces battery polarization, improves the multiplying power property of battery;It is able to maintain in battery core simultaneously warm between each battery unit The consistency of degree.
The semisolid lithium slurry battery is placed on electric vehicle, it is preferred that the electrode slice of semisolid lithium slurry battery with Ground is vertical and parallel with driving direction, in this way, with electric vehicle acceleration in the process of moving, slow down or pitch, every Inertia flowing can also occur from intracavitary electrolyte, be capable of the bridge joint of the intracavitary conductive particle formation of damage containment, avoid in battery Short circuit occurs for portion, improves the safety in utilization of power battery.
Present invention has an advantage that
1) electrocondution slurry forms an elastic conduction network between porous afflux anode layer, when battery is impacted by concussion When, the positive electrode material layer being bonded on porous anode collector is regardless of whether falling off or loosening, and active material particle is always Conductive contact is kept with electrocondution slurry, without losing conductive contact as conventional batteries, reduces battery capacity and service life;
2) in battery use process, the electrolyte shaken in separate cavities can destroy the bridge joint of conductive particle formation, keep away Exempt from inside battery and short circuit occurs, improves the safety in utilization of power battery;
3) this structure, which can be realized, carries out regular fluid infusion to battery or changes liquid, promotes battery cycle life and can safeguard Property.
Detailed description of the invention
Fig. 1 is semisolid lithium slurry battery principle figure of the present invention, wherein 101-sandwich anode composite pieces;102-contain lithium Negative electrode tab;103-porous afflux anode layers;104-electrocondution slurries;105-separate cavities;106-positive conductive particles;107— Separation layer;
Fig. 2 is the sandwich anode composite chip architecture schematic diagram of the present invention, wherein 201-insulated enclosure frames;202-positive poles Ear;
Fig. 3 is structural schematic diagram containing lithium cathode sheet of the invention, wherein 301-insulating trips;302-negative lugs;
Fig. 4 is the sandwich anode composite piece of the present invention and assembly structure diagram containing lithium cathode sheet;
Fig. 5 is battery core assembly structure diagram of the present invention, wherein 500-battery cores;
Fig. 6 is electrolyte covering plate structure schematic diagram of the present invention, wherein 600-electrolyte cover boards;601-liquid storage chambers; 602-injecting electrolytic solution mouths;
Fig. 7 is semisolid lithium slurry battery structure schematic diagram, wherein 700-semisolid lithium slurry batteries;701-anodes Cover board;702-negative covers;703-insulated enclosure cover boards;
Fig. 8 is semisolid lithium slurry battery testing data of the present invention, wherein figure (a), figure (b), figure (c), figure (d), figure (e), scheme (f), figure (g) is that separate cavities height is 0.2mm, 0.4mm, 0.6mm, 0.8mm, 1.0mm, 1.2mm, 1.4mm respectively Test data, the current density of battery are 3W/m2
Specific embodiment
With reference to the accompanying drawing, by embodiment, the present invention will be further described.
Embodiment one
The present embodiment provides a kind of semisolid lithium slurry batteries 700, including battery core 500, electrolyte cover board 600, positive cover Plate 701, negative cover 702 and insulated enclosure cover board 703.Wherein, battery core 500 includes several sandwich 101 Hes of anode composite piece Containing lithium cathode sheet 102, sandwich anode composite piece 101 and containing between lithium cathode sheet 102 be equipped with 0.5mm separate cavities 105, separate cavities Electrolyte is full of in 105.
Sandwich anode composite piece 101 includes porous afflux anode layer 103 and electrocondution slurry 104, porous afflux anode layer 103 It is made of the dual coating porous anode material layer of porous anode collector, is filled between two porous afflux anode layers The electrocondution slurry of 3mm thickness in the hole of electrocondution slurry partial penetration to porous afflux anode layer, forms sandwich anode composite Piece;It include negative current collector containing lithium cathode sheet, the two sides of negative current collector are equipped with the layer containing lithium titanate cathode material with a thickness of 0.5mm.
In the present embodiment, porous afflux anode layer is with a thickness of 500 μm, porosity 60%, and 0.5 μm of average pore size.
Porous afflux anode layer two sides are equipped with the separation layer for the electronic isolation being in close contact, and the thickness of separation layer is equal to isolation The one third of chamber thickness, separation layer the selection of material are non-woven fabrics of synthetic fiber.The main function of separation layer is to avoid positive and negative anodes It directly contacts and leads to internal short-circuit of battery.
Sandwich anode composite piece 101 is surrounded by insulated enclosure frame 201, prevents electrocondution slurry from sandwich anode composite piece Surrounding leakage, the material selection polytetrafluoroethylene (PTFE) of insulated enclosure frame.
Sandwich anode composite piece 101 is equipped with positive pole ear 202, and two of positive pole ear and sandwich anode composite piece are porous just The electrical connection of pole collector, and extend from sandwich anode composite piece, all positive pole ears are electrically connected and extend battery core in battery core; It is equipped with negative lug 302 containing lithium cathode sheet, negative lug is electrically connected with negative current collector, all negative lug electrical connections in battery core And extend battery core.
Positive cover board 701 in the present embodiment is equipped with the seal groove for accommodating positive pole ear, and positive pole ear prolongs out of seal groove Stretching is connect with external conductive;Negative cover 702 is equipped with the seal groove for accommodating negative lug, and negative lug extends out of seal groove It is connect out with external conductive.
The insulation cover plate 703 of semisolid lithium slurry battery in the present embodiment, positioned at the two sides of battery core electrode cavity, for pair The insulation and sealing of battery.
Two electrolyte cover boards 600 of the present embodiment semisolid lithium slurry battery are fixed on battery core separate cavities Inner electrolysis liquid stream Logical two sides, electrolyte cover board are equipped with injecting electrolytic solution mouth 602, are equipped with liquid storage chamber 601, liquid storage chamber 601 in electrolyte cover board Interior to be full of electrolyte, the liquid storage chamber is connected to the separate cavities of battery core.Separate cavities, the electrolyte cover board of semisolid lithium slurry battery Liquid storage chamber in be full of electrolyte, each section electrolyte is in connected state, therefore, can effectively improve each battery list of battery core The consistency of first electrolyte.
In the present embodiment, electrolyte cover board is equipped with PCT heating sheet, can will enter the heating of the electrolyte temperature in battery core 40 ℃。
Semisolid lithium slurry battery is placed on electric vehicle, wherein the electrode slice of semisolid lithium slurry battery and ground are hung down Direct join is substantially parallel with driving direction, in this way, with electric vehicle acceleration in the process of moving, slowing down or pitching, is isolated Inertia flowing can also occur for intracavitary electrolyte, be capable of the bridge joint of the intracavitary conductive particle formation of damage containment, avoid inside battery Short circuit occurs, improves the safety in utilization of power battery.
Embodiment two
In the present embodiment, the composition material of a few class positive electrode material layers, layer containing lithium titanate cathode material and electrocondution slurry, such as table are provided Shown in 1.
Table 1 forms the material of positive electrode material layer, layer containing lithium titanate cathode material and electrocondution slurry
Other contents of the present embodiment are the same as example 1.
Embodiment three
In the present embodiment, the material of a few class separation layers, porous anode collector and negative current collector is provided, as shown in table 2.
Table 2 forms the material of separation layer, porous anode collector and negative current collector
Other contents of the present embodiment are identical as embodiment one and embodiment two.
Example IV
In the present embodiment, a few class difference separate cavities height, electrocondution slurry thickness, porous afflux anode layer thickness, hole are provided Gap rate, average pore size scope and the degree of thickness containing lithium titanate cathode material.
2 separate cavities height of table, electrocondution slurry thickness, porous afflux anode layer thickness, porosity, average pore size scope, with And the degree of thickness containing lithium titanate cathode material
Other contents of the present embodiment are identical as embodiment one, embodiment two and embodiment three.
Embodiment five
The present embodiment provides one group of semisolid lithium slurry battery testing data, wherein separate cavities of semisolid lithium slurry battery Height is respectively 0.2mm, 0.4mm, 0.6mm, 0.8mm, 1.0mm, 1.2mm and 1.4mm, and the current density of battery is 3W/m2, electricity Pond positive electrode active materials are LiFePO4, and cathode is lithium metal, and electrocondution slurry is 30% carbon black and 70% electrolyte.Battery exists 3.4V(vs Li/Li+) nearby there is very flat charge and discharge platform, when separate cavities chamber height gradually increases, battery polarization electricity Pressure increases, and discharge capacity reduces.By attached drawing 8 as can be seen that battery maintains preferably when separate cavities height is less than 1.0mm Charge and discharge platform.
It is finally noted that the purpose for publicizing and implementing mode is to help to further understand the present invention, but ability The technical staff in domain is understood that without departing from the spirit and scope of the invention and the appended claims, various replacements and Modification is all possible.Therefore, the present invention should not be limited to embodiment disclosure of that, the scope of protection of present invention with Subject to the range that claims define.

Claims (10)

1. a kind of semisolid lithium slurry battery, including battery core, it is characterised in that: the battery core includes the folder that several are alternately placed Heart anode composite piece and contain lithium cathode sheet, sandwich anode composite piece and containing between lithium cathode sheet be equipped with height be 0.1~1mm every From chamber, electrolyte is full of in the separate cavities;The sandwich anode composite piece includes porous afflux anode layer and electrocondution slurry, more Hole afflux anode layer is made of the single or double of porous anode collector coating porous anode material layer, two porous collection The electrocondution slurry that 0~5mm thickness is filled between anode layer is flowed, part or all of electrocondution slurry penetrates into porous afflux anode layer Hole in, form sandwich anode composite piece;The sandwich anode composite piece is surrounded by insulated enclosure frame, and the insulation is close Seal frame be in " returning " shape, and with porous afflux anode layer edge fixing seal, prevent electrocondution slurry from sandwich four side of anode composite piece Leakage;The lithium cathode sheet that contains includes negative current collector, and the single or double of negative current collector is equipped with a thickness of 0.02~2mm's Layer containing lithium titanate cathode material, the layer containing lithium titanate cathode material are lithium metal, high lithium alloy or rich lithium inorganic non-metallic material.
2. semisolid lithium slurry battery as described in claim 1, it is characterised in that: the porous afflux anode layer with a thickness of 0.05~2.5mm, porosity be 30%~90%, 0.001 μm~10 μm of average pore size scope;The porous afflux anode layer Electrolyte and/or polymer dielectric are full of in hole, the polymer dielectric is polymeric matrix, liquid organic plasticizers With the gel polymer electrolyte composite material of the compound composition of lithium salts three parts.
3. semisolid lithium slurry battery as described in claim 1, it is characterised in that: the surface of the sandwich anode composite piece is set There is the separation layer of electronic isolation, and the thickness of the separation layer is less than or equal to 2/3rds of separate cavities thickness;Alternatively, described The surface of sandwich anode composite piece does not set separation layer;
The separation layer is polyethylene, polypropylene or Kynoar;Alternatively, separation layer is glass fibre non-woven, synthesis fibre Tie up non-woven fabrics or ceramic fiber paper;Alternatively, the material of separation layer uses the nonconducting polymeric matrix of electronics, the organic plasticising of liquid The gel polymer electrolyte composite material of agent and the compound composition of lithium salts three parts.
4. semisolid lithium slurry battery as described in claim 1, it is characterised in that: the sandwich anode composite piece is equipped with anode Tab, the positive pole ear are electrically connected with two porous anode collectors of sandwich anode composite piece, and from sandwich anode composite Piece extends, and all positive pole ears are electrically connected and extend battery core in battery core;It is described to be equipped with negative lug containing lithium cathode sheet, it is described Negative lug is electrically connected with negative current collector, and all negative lugs are electrically connected and extend battery core in battery core.
5. semisolid lithium slurry battery as described in claim 1, it is characterised in that: the porous anode material layer is that anode is living Property material: conductive agent: binder according to mass ratio for 59~98%:1~40%:1~10% be uniformly mixed;
The positive electrode active materials be LiFePO4, lithium manganese phosphate, lithium metasilicate, ferric metasilicate lithium, sulphate cpd, sulphur simple substance, Sulphur carbon complex, titanium sulphur compound, molybdenum sulfur compound, iron sulphur compound, doped lithium manganese oxide, lithium and cobalt oxides, lithium titanyl Compound, lithium-barium oxide, Li, Ni, Mn oxide, lithium nickel cobalt oxides, lithium nickel cobalt aluminum oxide, lithium nickel aluminum oxide, lithium nickel cobalt One of Mn oxide or lithium iron Ni, Mn oxide are a variety of.
6. semisolid lithium slurry battery as described in claim 1, it is characterised in that: the electrocondution slurry include electrolyte and The positive conductive particle that can be flowed in the electrolytic solution, wherein the mass ratio of positive conductive particle and electrocondution slurry be 10%~ 90%, average grain diameter is 500nm~500 μm;
The positive conductive particle is that one or more of conductive agent is compound, and the conductive agent is carbon black, Ketjen black, graphite Alkene, carbon nanotube, carbon fiber or amorphous carbon, compound mode include surface cladding, bonding or mechanical mixture;Alternatively, described Positive conductive particle be positive electrode active materials and above-mentioned conductive agent compound or mixture, wherein positive electrode active materials with lead The mass ratio of electric agent is 0~98%, and compound or mixed mode includes surface cladding, bonding or mechanical mixture.
7. semisolid lithium slurry battery as described in claim 1, it is characterised in that: the porous anode collector be with a thickness of 0.01~1000 μm of the electron conducting layer with through-hole structure, through-hole porosity are 10%~90%, pore diameter range 0.05mm~2mm;The porous anode collector is the porous mixture of conductive filler and binder, wherein conductive filler is Carbon black, carbon nanotube, carbon fiber, graphene, titanium valve, aluminium powder, alloy aluminium powder, stainless steel powder or silver powder, rich lithium silicon powder are closed containing lithium Bronze metalloid alloy conductive particle or be one or more of carbon material containing lithium, binder is polyvinyl chloride, poly- second Alkene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), polyester terephthalate, polyamide, polyimides, polyethers nitrile, polyacrylic acid One of methyl esters, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, sodium carboxymethylcellulose, improved polyalkene or Several, the mass fraction of conductive filler is not less than 70%;Alternatively, the porous anode collector is the metal with porous structure Conductive layer, metal wire knitted of the metal conducting layer by metal mesh, wire or surface with conductive carbon material coating form, mesh For polygon, including rectangular, diamond shape, rectangle;Alternatively, the metal conducting layer is the foam metal layer with porous structure, Or formed for expanded metal or metal foil through mechanical stamping or chemical attack, the material of metal conducting layer be aluminium, alloy aluminum, Stainless steel, silver, tin or titanium;Alternatively, the porous anode collector is conductive carbon fibre conductive fabric, wire and organic fiber silk Hybrid conductive cloth, surface coating conductive carbon material coating or the porous organic material for being coated with metallic film, it is described porous organic Material includes natural linen-cotton, terylene, aramid fiber, nylon, polypropylene fibre, polyethylene or polytetrafluoroethylene (PTFE), the wire and institute's plating metal The material of film is aluminium, alloy aluminum, stainless steel or silver;Alternatively, the porous anode collector is in above-mentioned several collectors Two or more any composed composite current collectors;
The negative current collector is the electron conducting layer with a thickness of 0.01~1000 μm, and the negative current collector is conductive metal Plate, metal foil, metal mesh or conductive fabric;The material of the conductive metal sheet, metal foil or metal mesh include copper, stainless steel, nickel, Titanium, silver, tin, tin-coated copper, nickel-clad copper or silver-plated copper;The surface of the metal plate, metal foil or metal mesh is coated with conductive carbon material Expect coating or the composite metal lithium by way of pressing or being electroplated;The conductive fabric be electric conduction of carbon fiber cloth, wire with it is organic Fiber filament hybrid conductive cloth, surface coating conductive carbon material coating or the porous organic material for being coated with metallic film, it is described porous Organic material includes natural linen-cotton, terylene, aramid fiber, nylon, polypropylene, polyethylene or polytetrafluoroethylene (PTFE).
8. semisolid lithium slurry battery as described in claim 1, it is characterised in that: the semisolid lithium slurry battery further includes Positive cover board, negative cover and insulation cover plate, the anode cover board are equipped with the seal groove for accommodating positive pole ear, and positive pole ear is from close Extend in sealing groove and is connect with external conductive;The negative cover is equipped with the seal groove for accommodating negative lug, and negative lug is from close Extend in sealing groove and is connect with external conductive;The insulation cover plate is located at the two sides of battery core electrode cavity.
9. semisolid lithium slurry battery as described in claim 1, it is characterised in that: the semisolid lithium slurry battery further includes Two electrolyte cover boards, the electrolyte cover board is fixed on the two sides of battery core separate cavities electrolyte inside circulation, on electrolyte cover board Equipped with injecting electrolytic solution mouth, it is equipped with liquid storage chamber in the electrolyte cover board, electrolyte, the liquid storage chamber and electricity are full of in liquid storage chamber The separate cavities of core are connected to.
10. semisolid lithium slurry battery as claimed in claim 9, it is characterised in that: the electrolyte cover board is equipped with heating dress It sets, the electrolyte temperature entered in battery core can be heated to 25~60 DEG C.
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