CN109155433A - A kind of secondary cell and preparation method thereof - Google Patents

A kind of secondary cell and preparation method thereof Download PDF

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Publication number
CN109155433A
CN109155433A CN201680085080.2A CN201680085080A CN109155433A CN 109155433 A CN109155433 A CN 109155433A CN 201680085080 A CN201680085080 A CN 201680085080A CN 109155433 A CN109155433 A CN 109155433A
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metal
battery
secondary cell
lithium
state electrolyte
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唐永炳
季必发
张帆
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to field of batteries more particularly to a kind of secondary cell and preparation method thereof.The secondary cell includes battery cathode, anode and all solid state electrolyte layer, and battery cathode includes negative current collector, does not include negative electrode active material；All solid state electrolyte layer is inorganic solid electrolyte；Anode includes plus plate current-collecting body and anode active material layer, and anode active material layer includes the positive electrode active materials of freely reversible deintercalate lithium ions, sodium ion or magnesium ion.Using all solid state electrolyte layer, it is not easy corroding electrode material, chemical stability can be maintained over a wide temperature range, increases the service life of battery；Battery volume is reduced, battery total quality is reduced, increases the energy density of battery without diaphragm using all solid state electrolyte layer simultaneously；Cancel negative electrode active material, not only reduces the cost of battery production, the effective battery capacity and energy density for improving battery, and show good charge-discharge performance.

Description

A kind of secondary cell and preparation method thereof Technical field
The present invention relates to field of batteries, in particular to a kind of secondary cell and preparation method thereof.
Background technique
Secondary cell is also referred to as rechargeable battery, is a kind of repeatable charge and discharge, using multiple battery.Compared to not re-usable one-shot battery, secondary cell has the advantages that use cost is low, environmental pollution is small.Current main secondary cell technology has lead-acid battery, Ni-Cr battery, nickel-metal hydride battery, lithium ion battery.It is wherein especially the most extensive with lithium ion battery applications.Lithium ion battery gradually becomes the power resources of the products such as electric car, electric tool due to having many advantages, such as that power density is high, self-discharge rate is low, memory-less effect and discharge voltage are stablized.The core building block of lithium ion battery generally comprises anode, cathode, electrolyte and diaphragm.General positive electrode usually has cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), LiMn2O4 (LiMn2O4), LiFePO4 (LiFePO4), lithium nickel cobalt dioxide binary material (LiNi1-xCoxO2), spinel structure (LiMn2-xMxO4, M=Ni, Co, Cr etc.), cobalt nickel lithium manganate ternary material [Li (Ni, Co, Mn) O2], the high manganese material [Li of stratiform richness lithium2MnO3-Li(NiCoMn)O2Deng.There is height ratio capacity at present, high voltage, what the battery of high-energy density almost used is all various liquid state organic electrolytes.Common liquid electrolyte there are specific energies low, perishable electrode material, the disadvantages such as design and assembly are difficult, safety is poor, service life is low.And in all batteries using liquid state organic electrolyte, it is necessary to use porous polymer membrane, the effect of diaphragm is to allow ion to pass through while physical isolation positive and negative anodes active material.Polyethylene or polypropylene film have the following problems as the diaphragm of battery: its poor heat resistance, meanwhile, in order to make film have enough intensity, film must have certain lower thickness limit, and which limits further increasing for battery capacity.If simple reduction film thickness, it will it causes the local strength of film insufficient, while will cause anomalad at high temperature, so, the reduction space of these film thicknesses is limited.And organic electrolyte secondary battery needs to further reduce volume, improves specific capacity and voltage, and need to further decrease the thickness of diaphragm.Therefore, it needs A kind of secondary cell is provided to solve common liquid electrolyte there are specific energies low, perishable electrode material, design and assembly are difficult, safety is poor, service life is low and must be using diaphragm the problems such as.Furthermore the cathode of conventional lithium ion battery must include negative electrode active material and negative current collector, and wherein negative electrode active material occupies substantial portion of volume and weight, constrains the battery capacity and energy density of lithium ion battery.
Summary of the invention
In order to overcome above-mentioned technical problem, the present invention provides a kind of secondary cell and preparation method thereof, it is intended to solve low specific energy existing for existing liquid electrolyte, perishable electrode material, design and assembly are difficult, safety is poor, service life is low and must be using diaphragm the problems such as.In addition, the present invention directly uses negative current collector as cathode, solve the problems, such as that battery capacity and energy density be not high.
First aspect, the present invention provides a kind of secondary cells, including battery cathode and anode；It is characterized in that, further including all solid state electrolyte layer, wherein
Battery cathode includes negative current collector, does not include negative electrode active material；The negative current collector includes metal, metal alloy or metal composite conductive material；
The all solid state electrolyte layer includes inorganic solid electrolyte；
The anode includes plus plate current-collecting body and anode active material layer, and the plus plate current-collecting body includes metal, metal alloy or metal composite conductive material, and the anode active material layer includes the positive electrode active materials of the reversible removal lithium embedded of energy, sodium or magnesium ion.
Preferably, the negative current collector includes the compound or in which any several alloy of one of aluminium, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
Preferably, the negative current collector is aluminium.
Preferably, the structure of the negative current collector is the porous aluminum of aluminium foil or porous aluminum or carbon material cladding or the multi-layer compound structure of aluminium.
Preferably, the plus plate current-collecting body includes the compound or in which any several alloy of one of aluminium, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
Preferably, the plus plate current-collecting body is aluminium.
Preferably, the inorganic solid electrolyte includes one or more of Ca-Ti ore type crystalline state electrolyte, anti-perovskite type crystalline state electrolyte, superionic conductors type crystalline state electrolyte, fast-ionic conductor type crystalline state electrolyte, carbuncle type crystalline state electrolyte or lithium nitride type crystalline state electrolyte, LiPON amorphous state electrolyte, amorphous sulfide amorphous state electrolyte and composite electrolyte.
Preferably, the positive electrode active materials include one or more of cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, lithium nickel cobalt dioxide binary material, spinel strucutre oxides, cobalt nickel lithium manganate ternary material, the high manganese material of stratiform richness lithium or in which the composite material of any one.
Preferably, the anode active material layer further includes conductive agent and binder, and the content of the positive electrode active materials is 60-95wt%, and the content of conductive agent is 0.1-30wt%, and the content of binder is 0.1-10wt%.
Second aspect, the present invention also provides a kind of preparation methods of secondary cell, this method comprises:
Prepare battery cathode, metal, metal alloy or metal composite conductive material are cut into required size, then the metal after cutting, metal alloy or metal composite conductive material surface are cleaned, using metal, metal alloy or metal composite conductive material after cleaning as battery cathode；
Solid electrolyte is prepared, above-mentioned inorganic solid electrolyte layer is cut into certain shapes and size is spare；
Prepare anode, positive polarity material, conductive agent and binder living are weighed by a certain percentage, it is added in appropriate solvent and is fully ground into uniform sizing material, then it is evenly applied to plus plate current-collecting body surface, it is cut after slurry is completely dried, the anode of size needed for obtaining, the positive electrode active materials are metal oxide or metallic compound；
It is assembled using the battery cathode, solid-state electrolyte layer and anode.
Compared with prior art, the beneficial effects of the present invention are: due to using solid-state electrolyte layer instead of common liquid state organic electrolyte, it is not easy corroding electrode material, chemical stability can be maintained over a wide temperature range, increase the service life of battery, and the security performance of battery is substantially increased, reduce battery Packaging cost, it is high when furthermore the diffusion velocity (ionic conductivity) of cation is compared with liquid electrolyte when solid-state, it could be theoretically argued that it can realize higher output；Due to, without diaphragm, reducing battery volume using solid-state electrolyte layer, reducing battery total quality, increasing the energy density of battery；Secondary cell provided by the invention cancels negative electrode active material simultaneously, it directlys adopt metal or metal alloy or metal composite while being used as cathode and collector, not only reduce the cost of battery production, simplify production technology, the battery capacity and energy density of battery can also be effectively improved simultaneously, and shows good charge-discharge performance.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of secondary cell provided in an embodiment of the present invention.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and detailed description.The following is a preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the principles of the embodiments of the present invention; several improvements and modifications can also be made, these modifications and embellishments are also considered to be within the scope of the present invention.
Figure one is the structural schematic diagram of secondary cell provided in an embodiment of the present invention.Referring to figure one, the embodiment of the invention provides secondary cell, including battery cathode 4, all solid state electrolyte layer 3 and anode, wherein battery cathode includes negative current collector, does not include negative electrode active material；Negative current collector is metal, metal alloy or metal composite conductive material.All solid state electrolyte layer includes inorganic solid electrolyte；The anode includes plus plate current-collecting body 1 and anode active material layer 2, plus plate current-collecting body is metal, metal alloy or metal composite conductive material, positive electrode active materials include the positive electrode active materials of the reversible deintercalate lithium ions of energy, sodium ion or magnesium ion, as long as lithium ion, sodium ion or magnesium ion is allowed freely to deviate from and insertion, such as binary or ternary transition metal oxide of lithium, the transition metal oxide of sodium or magnesium and its doping etc..
Secondary cell working principle provided in an embodiment of the present invention are as follows: secondary cell provided in an embodiment of the present invention is free of negative current collector, during the charging process, positive electrode active materials take off lithium, sodium or magnesium, directly react to form lithium-metal alloy, sodium-metal alloy or magnesium-metal alloy with the metal or metal alloy of cathode via all solid state electrolyte layer；In discharge process, passed through after lithium-metal alloy of cathode, sodium-metal alloy or de- lithium, sodium or magnesium It is embedded in positive electrode active materials by all solid state electrolyte layer, to realize charge and discharge process.
Secondary cell provided in an embodiment of the present invention, due to using all solid state electrolyte layer instead of common liquid state organic electrolyte, it is not easy corroding electrode material, chemical stability can be maintained over a wide temperature range, the service life of battery is increased, and substantially increases the security performance of battery, reduces the packaging cost of battery, furthermore high when the diffusion velocity (ionic conductivity) of cation is compared with liquid electrolyte when solid-state, it can realize higher output；Due to, without diaphragm, reducing battery volume using all solid state electrolyte layer, reducing battery total quality, increasing the energy density of battery；Secondary cell provided by the invention cancels negative electrode active material simultaneously, it directlys adopt metal or metal alloy or metal composite while being used as cathode and collector, not only reduce the cost of battery production, simplify production technology, the battery capacity and energy density of battery can also be effectively improved simultaneously, and shows good charge-discharge performance.
In the embodiment of the present invention, it is preferred that negative current collector includes the compound or in which any several alloy of one of aluminium, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.Further, the negative current collector is preferably aluminium.
In the embodiment of the present invention, it is furthermore preferred that negative current collector is the porous aluminum of aluminium foil or porous aluminum or carbon material cladding and the multilayer materials of other aluminium.The lithium ion for using porous aluminium foil positive electrode active materials being deviate from, reacts more abundant with metal aluminum alloy, improves battery capacity；Using the coated porous aluminium foil structure of carbon-coating in the case where improving battery capacity, because the protective effect of carbon-coating maintains the structure of aluminium foil, the cyclical stability of battery is further increased；It is also beneficial to inhibit and improve the Volumetric expansion of aluminium foil using multilayer aluminium composite material, improves cycle performance of battery.
In the embodiment of the present invention, it is preferred that plus plate current-collecting body includes the compound or in which any several alloy of one of aluminium, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.Further, the plus plate current-collecting body is preferably aluminium.
In embodiments of the present invention, the inorganic solid electrolyte includes Ca-Ti ore type crystalline state electrolyte, anti-perovskite type crystalline state electrolyte, superionic conductors type crystalline state electrolyte, fast-ionic conductor type crystalline state electrolyte, stone One or more of garnet type crystalline state electrolyte or lithium nitride type crystalline state electrolyte, LiPON amorphous state electrolyte, amorphous sulfide amorphous state electrolyte and composite electrolyte, such as can be Li0.5La0.5TiO3、Li3xLa2/3-xTiO3(x=0.11), Li3-x-δMx/2O(A1-zAz′)1-δ、Li3-n(OHn)Cl(0.83≤n≤2)、Li3-n(OHn)Br(1≤n≤2)、AM1M2P3O12(A=Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+、H+, H3O+, NH4 +, Cu+, Cu2+, Ag+, Pb2+, Cd2+, Mn2+, Co2+, Ni2+, Zn2+, Al3+, Ln3+(Ln is rare earth element), Ge4+, Zr4+, Hf4+Or vacancy；M=Zn2+、Cd2+、Ni2+、Mn2+、Co2+、Fe3+、Sc3+、Ti3+、V3+、Cr3+、Al3+、In3+、Ga3+、Y3+、Ln3+、Ti4+、Zr4+、Hf4+、Sn4+、Si4+、Ge4+、V5+、Nb5+、Ta5+、Sb5+、As5+)、Li2+2xZn1-xGeO4、Li3+xXxY1-xO4(X=Si, Sc, Ge, Ti；Y=P, As, V, Cr), Li3+xXxY1-xS4(X=Si, Sc, Ge, Ti；Y=P, As, V, Cr), Li5La3M2O12(M=Ta, Nb), Li3N、Li3N-LiXLiX (X=Cl, Br, I), Li9-nxMxN2Cl3(M=Na, K, Rb, Cs, Mg, Al), 3Li3N-MI (M=Li, Na, K), LiPON, Li2S、Li2S-MxSy(M=Al, Si, P), Li2S-SiS2-LixMOy(M=Si, P, B, Al, Ga, In), Li2S-P2S5、Al2O3With one or more of LiI and other type complex.
Preferably, in the embodiment of the present invention, as long as the positive electrode active materials in positive-active layer are it is not also specifically limited, being capable of reversible abjection or insertion anion.For example, positive electrode active materials are selected from cobalt acid lithium (LiCoO if inorganic solid electrolyte is lithium salts electrolyte2), lithium nickelate (LiNiO2), LiMn2O4 (LiMn2O4), LiFePO4 (LiFePO4), lithium nickel cobalt dioxide binary material (LiNi1-xCoxO2), spinel structure (LiMn2-xMxO4, M=Ni, Co, Cr etc.), cobalt nickel lithium manganate ternary material [Li (Ni, Co, Mn) O2], the high manganese material [Li of stratiform richness lithium2MnO3-Li(NiCoMn)O2], the Li of NASCION structure3M2(PO4)3One or more of (M=V, Fe, Ti etc.) etc. the or in which composite material of any one.If inorganic solid electrolyte is sodium salt electrolyte, positive electrode active materials can be the phosphoric acid salt polyanionic compound of sodium, the iron cyanide and its Prussian blue complex, active redox polymer, tunnel structure compound, spinel oxides, stratiform transiting metal oxidation The one or more of object.Such as: it can be Na2V3(PO4)3、Na2Zn3[Fe(CN)6]2`xH2O、Na2Fe(SO4)2、NaMn2O4、Na0.61[Mn0.27Fe0.34Ti0.39]O2、NaCoO2One or more of.
In the embodiment of the present invention, anode active material layer further includes conductive agent and binder, and the content of positive electrode active materials is 60-95wt%, and the content of conductive agent is 0.1-30wt%, and the content of binder is 0.1-10wt%.Meanwhile conductive agent and binder are not particularly limited, using commonly used in the art.Conductive agent is one of conductive black, Super P conduction carbon ball, electrically conductive graphite KS6, carbon nanotube, conductive carbon fibre, graphene, redox graphene or a variety of.Binder is one of Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, polyolefins or a variety of.
Second aspect, the embodiment of the invention also provides the methods for preparing above-mentioned secondary cell, comprising:
Step 101, preparation battery cathode.
Metal, metal alloy or metal composite conductive material are cut into required size, then the metal after cutting, metal alloy or metal composite conductive material surface are cleaned, using metal, metal alloy or metal composite conductive material after cleaning as battery cathode；
Specifically, metal, metal alloy or metal composite conductive material include the compound or in which the alloy of any one of one of aluminium, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal, can be metal or metal alloy paillon.
Step 102 prepares solid electrolyte, and above-mentioned inorganic solid electrolyte layer is cut into certain shapes and size is spare；
Step 103 prepares anode.Preparing anode includes: to weigh positive polarity material, conductive agent and binder living by a certain percentage, it is added in appropriate solvent and is fully ground into uniform sizing material, then it is evenly applied to plus plate current-collecting body surface, it is cut after slurry is completely dried, the anode of size needed for obtaining, the positive electrode active materials are metal oxide or metallic compound.
Preferably, if inorganic solid electrolyte be lithium salts electrolyte, can deintercalate lithium ions positive electrode active materials It can be selected from cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), LiMn2O4 (LiMn2O4), LiFePO4 (LiFePO4), lithium nickel cobalt dioxide binary material (LiNi1-xCoxO2), spinel structure (LiMn2-xMxO4, M=Ni, Co, Cr etc.), cobalt nickel lithium manganate ternary material [Li (Ni, Co, Mn) O2], the high manganese material [Li of stratiform richness lithium2MnO3-Li(NiCoMn)O2], the Li of NASCION structure3M2(PO4)3One or more of (M=V, Fe, Ti etc.) etc. or its composite material.
Step 104 is assembled using the battery cathode, all solid state electrolyte layer and anode.
Preferably, under inert gas or anhydrous and oxygen-free environment, by the cathode prepared, solid-state or gel state electrolyte layer, anode successively Close stack, it is then encapsulated into battery case, completes battery assembly.
It should be noted that although above-mentioned steps 101-103 is to describe the operation of preparation method of the present invention with particular order, this does not require that or implies must execute these operations in this particular order.The preparation of step 101-103 simultaneously or arbitrarily can be executed successively.
The secondary cell preparation method and aforementioned secondary cell are that based on the same inventive concept, have the institute of aforementioned secondary cell effective using the secondary cell that the secondary cell preparation method obtains, details are not described herein.
Above-mentioned secondary cell preparation method is further illustrated below by specific embodiment, it should be understood, however, that, these embodiments, which are only used for being described in more detail, to be used, and but should not be understood as present invention is limited in any form.
Embodiment 1
Preparation battery cathode: the aluminium foil with a thickness of 0.02mm is taken, the disk of diameter 12mm is cut into, cleans aluminium foil with ethyl alcohol, is dried spare as negative current collector.
Solid electrolyte is prepared, by Li0.5La0.5TiO3Electrolyte layer is cut into certain shapes and size is spare；.
Prepare anode: 0.4g cobalt acid lithium, 0.05g carbon black, 0.05g Kynoar be added to 2m] in N-methyl pyrrolidone solution, it is fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
Battery assembly: in the glove box of inert gas shielding, by the above-mentioned negative current collector prepared, entirely Then above-mentioned stacking portion is encapsulated into button cell shell by solid-state electrolyte layer, anode successively Close stack, complete battery assembly.
Embodiment 2-26
Embodiment 2-26 and 1 secondary cell preparation process step of embodiment are same as Example 1, and difference is to prepare the difference of material difference or material content, referring specifically to table 1.
1 embodiment 1-26 negative electrode material of table, positive electrode and solid-state electrolyte layer comparison
Comparative example
Preparation battery cathode: 0.4g graphite is taken, 0.05g carbon black, 0.05g Kynoar are added in 2ml N-methyl pyrrolidone solution, are fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as battery cathode after compacting.
It prepares diaphragm: high molecular polythene is cut into the disk of diameter 16mm, it is spare as diaphragm after drying.
Prepare electrolyte: weighing 0.75g lithium hexafluoro phosphate and be added to) it is added in 2.5ml ethylene carbonate and 2.5ml dimethyl carbonate, it is stirred well to after lithium hexafluoro phosphate is completely dissolved spare as electrolyte.
It prepares anode: 0.4g lithium cobaltate cathode material, 0.05g carbon black, 0.05g Kynoar being added in 2ml N-methyl pyrrolidone solution, acquisition uniform sizing material is fully ground；Then slurry is evenly applied to aluminium foil surface and be dried in vacuo.The disk of diameter 10mm is cut into dry the electrode obtained piece, it is spare as anode after compacting.
Battery assembly: in the glove box of inert gas shielding; by the above-mentioned negative current collector prepared, diaphragm, anode successively Close stack; electrolyte, which is added dropwise, makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into button cell shell, completes battery assembly.
The performance test of battery:
Charge-discharge tests: the secondary cell prepared in above-mentioned secondary cell preparation method embodiment is passed through to the constant current charging of 100mA/g positive electrode active materials, until its voltage reaches 4.8V, then with identical current discharge, until its voltage reaches 3V, measure its battery capacity and energy density, its cyclical stability is tested, is indicated with circulating ring number, circulating ring number refers to battery institute charge and discharge number when battery capacity decays to 85%.
3 battery performance test result of table
It was found from above-mentioned experimental data: 1-6 of the embodiment of the present invention uses different negative electrode materials (negative current collector) and the positive active material of different component, in contrast, embodiment 6 is optimal as the circulating ring number of the battery of negative current collector using the coated porous aluminium of carbon-coating, in contrast, use porous aluminum as the embodiment 5 of negative electrode material than using aluminium foil to obtain bigger battery capacity as the embodiment 1 of negative electrode material.
With identical negative current collector, embodiment 7-12 uses different positive electrode active materials, is being used cooperatively corresponding inorganic solid electrolyte, is all realizing the cycle performance of good battery capacity and battery.
With identical negative current collector and positive electrode active materials, embodiment 12,17,18,19 Using different inorganic solid electrolytes, the cycle performance of good battery capacity and battery is all realized.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto, and the variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to scope of the present invention.

Claims (10)

  1. A kind of secondary cell, including battery cathode and anode；It is characterized in that, further including all solid state electrolyte layer, wherein
    Battery cathode includes negative current collector, does not include negative electrode active material；The negative current collector includes metal, metal alloy or metal composite conductive material；
    The all solid state electrolyte layer includes inorganic solid electrolyte；
    The anode includes plus plate current-collecting body and anode active material layer, the plus plate current-collecting body includes metal, metal alloy or metal composite conductive material, and the anode active material layer includes the positive electrode active materials of the reversible deintercalate lithium ions of energy, sodium ion or magnesium ion.
  2. Secondary cell as described in claim 1, which is characterized in that the negative current collector includes the compound or in which the alloy of any one of one of aluminium, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
  3. Secondary cell as claimed in claim 2, which is characterized in that the negative current collector is preferably aluminium.
  4. Secondary cell as claimed in claim 3, which is characterized in that the structure of the negative current collector is the porous aluminum of aluminium foil or porous aluminum or carbon material cladding or the multi-layer compound structure of aluminium.
  5. Secondary cell as described in claim 1, which is characterized in that the plus plate current-collecting body includes the compound or in which the alloy of any one of one of aluminium, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese or in which any one metal.
  6. Secondary cell as claimed in claim 5, which is characterized in that the plus plate current-collecting body is preferably aluminium.
  7. Secondary cell as described in claim 1, it is characterized in that, the inorganic solid electrolyte includes one or more of Ca-Ti ore type crystalline state electrolyte, anti-perovskite type crystalline state electrolyte, superionic conductors type crystalline state electrolyte, fast-ionic conductor type crystalline state electrolyte, carbuncle type crystalline state electrolyte, lithium nitride type crystalline state electrolyte, LiPON amorphous state electrolyte, amorphous sulfide amorphous state electrolyte and composite electrolyte.
  8. Secondary cell as described in one of claim 1-7, which is characterized in that the positive electrode active materials Including one or more of cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, lithium nickel cobalt dioxide binary material, spinel strucutre oxides, cobalt nickel lithium manganate ternary material, the high manganese material of stratiform richness lithium or in which the composite material of any one.
  9. Secondary cell as described in one of claim 1-7, it is characterized in that, the anode active material layer further includes conductive agent and binder, the content of the positive electrode active materials is 60-95wt%, the content of conductive agent is 0.1-30wt%, and the content of binder is 0.1-10wt%.
  10. A kind of preparation method preparing secondary cell as claimed in one of claims 1 to 9, characterized by comprising:
    Prepare battery cathode, metal, metal alloy or metal composite conductive material are cut into required size, then the metal after cutting, metal alloy or metal composite conductive material surface are cleaned, using metal, metal alloy or metal composite conductive material after cleaning as battery cathode；
    Solid electrolyte is prepared, above-mentioned inorganic solid electrolyte layer is cut into certain shapes and size is spare；
    Prepare anode, positive polarity material, conductive agent and binder living are weighed by a certain percentage, it is added in appropriate solvent and is fully ground into uniform sizing material, then it is evenly applied to plus plate current-collecting body surface, it is cut after slurry is completely dried, the anode of size needed for obtaining, the positive electrode active materials are metal oxide or metallic compound；
    It is assembled using the battery cathode, solid electrolyte and anode.
CN201680085080.2A 2016-05-06 2016-05-06 A kind of secondary cell and preparation method thereof Pending CN109155433A (en)

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