CN109037591A - Electrode and all-solid-state battery and preparation method thereof and lithium ion battery - Google Patents
Electrode and all-solid-state battery and preparation method thereof and lithium ion battery Download PDFInfo
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- CN109037591A CN109037591A CN201810869788.8A CN201810869788A CN109037591A CN 109037591 A CN109037591 A CN 109037591A CN 201810869788 A CN201810869788 A CN 201810869788A CN 109037591 A CN109037591 A CN 109037591A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- 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 provides a kind of electrode and all-solid-state battery and preparation method thereof and lithium ion batteries, are related to battery technology field, which includes the conductive foams as support body framework and be filled in the intrapore electrode active material of conductive foams.The all-solid-state battery, including cathode, anode and electrolyte；Wherein, anode includes conductive foams and is filled in the intrapore positive electrode active materials of conductive foams；Cathode is Carbon foam, or, cathode includes conductive foams and is filled in the intrapore negative electrode active material of conductive foams；Solid electrolyte is coated on positive electrode surface and/or negative terminal surface.The low problem of existing rechargeable battery energy density can be alleviated using the electrode and all-solid-state battery, reach the technical effect for improving battery energy density.
Description
Technical field
The present invention relates to battery technology fields, more particularly, to a kind of electrode and all-solid-state battery and preparation method thereof and lithium
Ion battery.
Background technique
Secondary cell, also known as rechargeable battery, such as lithium battery are the accumulation power supplies of a new generation, with rechargeable battery
The continuous renewal and development of technology, rechargeable battery has been widely used in the every field in life at present, especially new
There is very big application prospect in the fields such as energy automobile, power grid energy storage, special purpose vehicle and communication base station.
The structure of the rechargeable battery of liquid electrolyte composition generally comprise the anode of successively lamination setting, electrolyte, every
Film and cathode.The structure of all solid state rechargeable battery generally comprises anode, solid electrolyte and the cathode of successively lamination setting.
Wherein anode and cathode respectively include collector and positive electrode active materials or negative electrode active material coated in collection liquid surface, collect
Fluid is generally aluminium foil or copper foil, which is the non-active ingredient of battery, and main function is to be used for transmission carrier.Each
Just there are two layers of collector (respectively plus plate current-collecting body and negative current collector), the weight of collector in the battery core unit of rechargeable battery
Amount occupies 10% or more of total secondary cell weight, with the increase of anode in secondary cell and the cathode setting number of plies, this portion
The weight divided also increases with it.
When evaluating the electrical performance indexes of rechargeable battery, energy density is an important reference index.With electronic vapour
For vehicle, light capacity but also big battery are just able to satisfy the requirement of electric car to weight not only, carry the battery of same weight, energy is close
Spending higher vehicle just can run remoter.Therefore, the energy density for how improving secondary cell becomes the research heat of current secondary cell
Point.
Summary of the invention
The first object of the present invention is to provide a kind of electrode and preparation method thereof, utilizes the electrode assembling rechargeable battery
It is able to solve the low technical problem of rechargeable battery energy density in the prior art.
The second object of the present invention is to provide a kind of all-solid-state battery and preparation method thereof, to alleviate the complete of the prior art
The low problem of solid state battery energy density.
The third object of the present invention is to provide a kind of lithium ion battery comprising liquid electrolyte, to alleviate the prior art
The low problem of lithium ion battery energy density.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of electrode, the electrode include the conductive foams as support body framework and are filled in the conductive foam
The intrapore electrode active material of material；Wherein, the electrode active material is positive electrode active materials or negative electrode active material.
Further, the conductive foams are Carbon foam or foam metal；
Preferably, percent opening >=95% of the conductive foams.
A kind of preparation method of electrode, the conductive foams as support body framework are soaked in containing electrode activity material
In the solution of material, electrode is obtained after drying；Wherein, the electrode active material is positive electrode active materials or negative electrode active material
Material.
Further, the foam conductive material is Carbon foam or foam metal.
Further, the Carbon foam is to obtain after the polymer with foaming structure is carried out carbonization treatment；
Preferably, the polymer is melamine or melamine derivative；Wherein, carburizing temperature is 600~900
DEG C, carbonization time is 1~6h.
A kind of all-solid-state battery, including cathode, anode and electrolyte；Wherein,
The anode includes conductive foams and is filled in the intrapore positive electrode active materials of the conductive foams；
The cathode is Carbon foam, or, the cathode includes conductive foams and is filled in the conductive foams
Intrapore negative electrode active material.
Further, the solid electrolyte is coated on the positive electrode surface and/or the negative terminal surface.
Further, the conductive foams are Carbon foam or foam metal；
Preferably, percent opening >=95% of the conductive foams.
A kind of preparation method of all-solid-state battery, comprising steps of
Step S1: conductive foams are soaked in the solution containing negative electrode active material, obtain cathode after dry, or
Directly using Carbon foam as cathode；
Step S2: conductive foams are soaked in the solution containing positive electrode active materials, obtain anode after dry；
Step S3: anode and/or cathode are soaked in the solution containing solid electrolyte and binder, are completed after dry
The electrolyte of electrode coats；
Step S4: it being assembled after anode and cathode superposition using hot pressing mode, wherein temperature is 240~290 DEG C,
Pressure is 5~20MPa, and the time is 0.5~2h.
Further, the conductive foams are Carbon foam or foam metal；
Preferably, percent opening >=95% of the conductive foams.
A kind of lithium ion battery, comprising: cathode, anode, electrolyte and diaphragm；Wherein,
The anode includes conductive foams and is filled in the intrapore positive electrode active materials of the conductive foams；
The cathode is Carbon foam, or, the cathode includes conductive foams and is filled in the conductive foams
Interior negative electrode active material；
Preferably, the conductive foams are Carbon foam or foam metal；
Preferably, percent opening >=95% of the conductive foams.
Compared with the prior art, the invention has the following beneficial effects:
Electrode provided by the invention is employed as the conductive foams of support body framework as matrix, then by electrode active
Property material is filled in the conductive foams.With conductive foams instead of original collector in the structure, due to leading
Electric foamed material is porous structure, and bulk density is very low, compared with the electrode of traditional current collector structure, prepares condition of equivalent thickness
Electrode, the weight of the inert matter needed significantly reduces, therefore using conductive foams as electrode active material
The weight of electrode can be significantly reduced in carrier, and then promotes the energy density of rechargeable battery.
In all-solid-state battery provided by the invention, above-mentioned electrode structure is can be used in anode and/or cathode, wherein anode
Including the conductive foams as support body framework and it is filled in the intrapore positive electrode active materials of conductive foams；Cathode
For Carbon foam, alternatively, cathode includes the conductive foams as support body framework and is filled in conductive foams hole
Negative electrode active material.In the all-solid-state battery, equally with conductive foams instead of original collector directly as leading
The carrier of electrode or electrode active material, since the bulk density of conductive foams is close far below the volume of metal foil
Therefore degree using conductive foams directly as electrode or as the carrier of electrode active material, can effectively mitigate entire
The weight of all-solid-state battery, and then improve the energy density of all-solid-state battery.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the SEM structural schematic diagram of conductive foams in one embodiment of the present invention；
Fig. 2 is the structural schematic diagram of the lithium ion battery of one embodiment of the present invention；
Fig. 3 is the structural schematic diagram of the all-solid-state battery of one embodiment of the present invention.
Wherein, 10- aluminum plastic film；20- cathode；30- anode；40- electrolyte；50- diaphragm；60- solid electrolyte.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
On the one hand, the present invention provides a kind of electrodes, including the conductive foams as support body framework and are filled in
The intrapore electrode active material of conductive foams, wherein electrode active material is positive electrode active materials or negative electrode active material
Material.
Electrode provided by the invention is employed as the conductive foams of support body framework as matrix, then by electrode active
Property material is filled in the hole of the conductive foams.With conductive foams instead of original collector in the structure,
Since conductive foams are porous structure, bulk density is very low, and compared with the electrode of traditional current collector structure, preparation is same
The weight of the electrode of equal thickness, the inert matter needed significantly reduces, therefore using conductive foams as electrode activity
The weight of electrode can be significantly reduced in the carrier of material, and then promotes the energy density of rechargeable battery.
In the present invention, conductive foams have three-dimensional frame structure, for example, its structure can use as shown in Figure 1
Structure, there are a large amount of hole, percent opening for example can be 90% or more, together for the inside and surface of the three-dimensional frame structure
When, which has certain rigidity, being capable of structural breakdown of the load electrode active material without making its own.
Electrode in the present invention can be anode or cathode, when electrode is anode, the just extremely conductive foam
Material and the intrapore positive electrode active materials of conductive foams are filled in, for example, positive electrode active materials can be lithium salts, sodium
Salt, zinc salt, sulphur or metal sulfide etc.；When electrode is cathode, which is conductive foams and is filled in conductive foam
The intrapore negative electrode active material of material, such as can be alkali metal and its alloy, silicium cathode material or silicon-carbon cathode material etc..
Wherein, positive electrode active materials or negative electrode active material can be selected according to the concrete type of battery, not do specific limit herein
It is fixed.
In the present invention, conductive foams for example can be Carbon foam or foam metal, preferably Carbon foam.Carbon foam and
Foam metal all has electric conductivity and has certain rigidity, can fill electrode active in the hole of foam as foaming structure
Property material.Since the density of Carbon foam is smaller, the weight of conductive foams can be further decreased, therefore, in the present invention, is led
Electric foamed material is preferably Carbon foam.
In certain embodiments of the present invention, percent opening >=95% of conductive foams, preferably 98%.Conduction bubble
The percent opening of foam material is higher, and portative electrode active material amount can be more, and the energy that can be further improved battery is close
Degree.
On the other hand, the present invention provides a kind of preparation methods of above-mentioned electrode, and the conduction as support body framework is steeped
Foam material is soaked in the solution containing electrode active material, obtains electrode after drying；Wherein, the electrode active material is
Positive electrode active materials or negative electrode active material.
In the present invention, some binders can be added when configuring the solution of electrode active material, binder can be selected
One or more of polycarbonate-based binder, such as poly- ethylene carbonate, polymerized thylene carbonate vinyl acetate or polypropylene carbonate.
The quasi polymer is environmentally protective, biodegradable.Solvent can be one in anhydrous acetonitrile, benzene, methyl phenyl ethers anisole or dehydrated alcohol etc.
Kind.
The configuration method of solution containing electrode active material for example can be with are as follows: binder is dissolved in solvent, then plus
Enter electrode active material, after mixing evenly, obtains then being immersed in conductive foams with the homogeneous solution of certain viscosity
Air drying in above-mentioned solution；Above step is repeated later several times, and the load capacity of electrode active material is made to reach maximum.Its
In, the mass ratio of binder and electrode active material is 3~6:100.
In certain embodiments of the present invention, conductive foams for example can be Carbon foam or foam metal, foam
Charcoal and foam metal all have electric conductivity and have certain rigidity, and electricity can be filled in the hole of foam as foaming structure
Pole active material.Since the density of Carbon foam is smaller, the weight of conductive foams can be further decreased, therefore, the present invention
In, conductive foams are preferably Carbon foam.
In certain embodiments of the present invention, Carbon foam is after having the polymer of foaming structure to carry out carbonization treatment
It obtains.Further, the polymer that can use spongelike structure carries out carbonization treatment, obtains conductive foams.Wherein, gather
Closing object can be melamine, melamine derivative, polyethylene, polyurethane or polystyrene etc., preferably melamine
Or melamine derivative.Since melamine foamed plastic and melamine derivative foam have higher percent opening, when
When polymer selects melamine foamed plastic and melamine derivative foam, the percent opening of obtained conductive foams is higher.
Avalanche deformation will not occur for the polymer of foaming structure its foam frame structure after carbonization treatment, that is, still have after being carbonized a large amount of
Cavity, while having sufficiently strong electric conductivity.And carbonization treatment is carried out in the polymer of spongelike structure using itself, it obtains
Hole is more uniformly spread unanimously.The process of carbonization treatment for example can be, under protective atmosphere, by the melamine of foaming structure
Amine or melamine derivative carry out carbonization treatment, obtain conductive foams, i.e. Carbon foam；Wherein carburizing temperature be 600~
900 DEG C, preferably 700~800 DEG C, 1~6h of carbonization time, preferably 2~4h.The conductive foams obtained using this method
Percent opening is up to 99% or more, SEM figure as shown in Figure 1, from figure 1 it appears that the percent opening of the Carbon foam is very high, and
Hole is evenly distributed unanimously, and three-dimensional netted connection structure is formed between Carbon Materials, it is made still to possess relatively high conductivity.
The third aspect, the present invention provides a kind of all-solid-state batteries, including cathode, anode and electrolyte；Wherein,
Anode includes conductive foams and is filled in the intrapore positive electrode active materials of conductive foams；
Cathode is Carbon foam, or, cathode includes conductive foams and is filled in the intrapore cathode of conductive foams
Active material；
Solid electrolyte is coated on positive electrode surface and/or negative terminal surface.
In all-solid-state battery provided by the invention, above-mentioned electrode structure is can be used in anode and/or cathode, wherein anode
Including the conductive foams as support body framework and it is filled in the intrapore positive electrode active materials of conductive foams；Cathode
For Carbon foam, alternatively, cathode includes the conductive foams as support body framework and is filled in conductive foams hole
Negative electrode active material.In the all-solid-state battery, equally with conductive foams instead of original collector directly as leading
The carrier of electrode or electrode active material, since the bulk density of conductive foams is close far below the volume of metal foil
Therefore degree using conductive foams directly as electrode or as the carrier of electrode active material, can effectively mitigate entire
The weight of all-solid-state battery, and then improve the energy density of all-solid-state battery.
In traditional all-solid-state battery, there are a large amount of gap between anode, cathode and solid electrolyte, in order to avoid
Occur short circuit phenomenon between positive electrode and negative electrode, the width of solid electrolyte it is wider than positive and negative anodes go out several millimeters, while in tab
The side of extraction will also reserve certain space for soldering polar ear, this wastes a large amount of space, leads to battery volume energy
The reduction of density.
To solve the above problems, in the present invention, solid electrolyte is coated on positive electrode surface and/or negative terminal surface.
Solid electrolyte is set to the surface of cathode or anode in the form coated, it is possible to reduce cathode and electrolyte or just
The tightness of its contact is improved in the distance between pole and electrolyte.The structure is totally different from traditional anode, cathode
Design structure instead cathode, anode and electrolyte between electrolyte intersect, and considerably reduce electricity
Space waste inside pond, to improve the mass energy density and volume energy density of battery.
For example, in certain embodiments of the present invention, cathode is conductive foams, just extremely conductive foams and
The positive electrode active materials being filled in conductive foams；Solid electrolyte is coated on negative terminal surface.
One layer of solid electrolyte is uniformly coated in negative terminal surface, the distance between positive and negative anodes can be made very close, at this point, wanting
Seeking the cladding of solid electrolyte, there is no any flaws, otherwise can be easy to cause battery short circuit；The electrolyte layer coated simultaneously is also
Cannot be too thick, so that cathode is kept original open-celled structure.
In the present invention, conductive foams for example can be Carbon foam or foam metal, preferably Carbon foam.Carbon foam and
Foam metal all has electric conductivity and has certain rigidity, can fill electrode in the hole of foam as after foaming structure
Active material.Since the density of Carbon foam is smaller, the weight of conductive foams can be further decreased, therefore, in the present invention,
Conductive foams are preferably Carbon foam.
Conductive foams, especially Carbon foam, material percent opening itself is high, and loading is big, is made using Carbon foam
When all-solid-state battery, positive cathode is easy to intersect, and is conducive to anode and cathode contact, reduces interface resistance.
In certain embodiments of the present invention, percent opening >=95% of conductive foams, preferably 98%.Conduction bubble
The percent opening of foam material is higher, and portative electrode active material amount can be more, can be further improved all-solid-state battery
Energy density.
Fourth aspect, the present invention provides a kind of preparation methods of all-solid-state battery, comprising steps of
Step S1: conductive foams are soaked in the solution containing negative electrode active material, obtain cathode after dry, or
Directly using Carbon foam as cathode；
Step S2: conductive foams are soaked in the solution containing positive electrode active materials, obtain anode after dry；
Step S3: anode and/or cathode are soaked in the solution containing solid electrolyte and binder, are completed after dry
The electrolyte of electrode coats；
Step S4: it being assembled after anode and cathode superposition using hot pressing mode, wherein temperature is 240~290 DEG C,
Pressure is 5~20MPa, and the time is 0.5~2h.
Wherein, conductive foams for example can be Carbon foam or foam metal.The percent opening of conductive foams >=
95%.
In the preparation method of all-solid-state battery of the invention, when cathode is conductive foams and is filled in conductive foam
When negative electrode active material in material, conductive foams are soaked in the solution containing negative electrode active material, then through dry
Cathode is obtained after dry；Or directly using Carbon foam as cathode.
It, will be conductive when just extremely conductive foams and when being filled in the intrapore positive electrode active materials of conductive foams
Foamed material is soaked in the solution containing positive electrode active materials, then obtains anode after drying.
Utilize the cathode of the preparation method both available filling negative electrode active material, also available filling positive-active
The anode of material, according to specifically being prepared.
Wherein, the preparation method of conductive foams for example can be with are as follows: the polymer with foaming structure is carbonized
Processing, obtains conductive foams；Further, the preparation method of conductive foams include: will be with spongelike structure
Polymer carries out carbonization treatment, obtains conductive foams.Wherein, polymer can for melamine, melamine derivative,
Polyethylene, polyurethane or polystyrene etc., preferably melamine or melamine derivative.Due to melamine foamed plastic and
Melamine derivative foam has higher percent opening, therefore, when polymer selects melamine foamed plastic and melamine to spread out
When bio foam, the percent opening of obtained conductive foams is higher.The polymer of foaming structure its foam after carbonization treatment
Avalanche deformation will not occur for frame structure, that is, still have a large amount of cavity after being carbonized, while having sufficiently strong electric conductivity.And it utilizes
Itself carries out carbonization treatment in the polymer of spongelike structure, and obtained hole is more uniformly spread unanimously.For example, in protection gas
Under atmosphere, the melamine of spongelike structure or melamine derivative are subjected to carbonization treatment, conductive foams is obtained, that is, steeps
Foam charcoal；Wherein carburizing temperature be 600~900 DEG C, preferably 700~800 DEG C, 1~6h of carbonization time, preferably 2~4h.It utilizes
The conductive foams percent opening that this method obtains be up to 99% or more, SEM figure as shown in Figure 1, from figure 1 it appears that
The percent opening of the Carbon foam is very high, and hole is evenly distributed unanimously, forms three-dimensional netted connection structure between Carbon Materials, makes it
Still possess relatively high conductivity.
In the present invention, anode and/or cathode are soaked in the solution containing solid electrolyte and binder, it is complete after dry
It is coated at the electrolyte of electrode.Wherein, some binders can be added when configuring the solution of solid electrolyte, binder can be with
Selected from one of polycarbonate-based binder, such as poly- ethylene carbonate, polymerized thylene carbonate vinyl acetate or polypropylene carbonate or
It is several.The quasi polymer is environmentally protective, biodegradable.Solvent can be in anhydrous acetonitrile, benzene, methyl phenyl ethers anisole or dehydrated alcohol etc.
One kind.
The configuration method of solution containing solid electrolyte for example can be with are as follows: binder is dissolved in solvent, is then added
Solid electrolyte obtains the homogeneous solution with certain viscosity, then by the conductive foams as cathode after mixing evenly
It is immersed in the cladding that air drying in above-mentioned solution completes cathode.Wherein, the mass ratio of binder and electrode active material be 3~
6:100。
By taking all solid state lithium ion type battery as an example, in certain embodiments of the present invention, cathode is conductive foams,
Just extremely conductive foams and the positive electrode active materials being filled in conductive foams, are coated on cathode for solid electrolyte
Then surface is assembled cathode, anode and electrolyte to obtain all-solid-state battery.Wherein, positive electrode active materials are, for example, cobalt
Any one of sour lithium, lithium nickelate, LiMn2O4, LiFePO4 or nickle cobalt lithium manganate or at least two combination.In order to reduce just
Interface resistance between pole active material and solid electrolyte, positive electrode active materials can pass through coating modification, such as with
LiNbO3Coat LiCoO2。
In above embodiment, solid electrolyte is coated on the method for coating of negative terminal surface the following steps are included: by cathode
It is dipped in the solution containing solid electrolyte and binder, then takes out the electrolyte cladding of completion cathode after drying.Using molten
The available uniform solid electrolyte clad of method for coating of liquid immersion re-dry.
In the present invention, assembling process is by anode with the cathode of solid electrolyte cladding or by cathode and solid electrolyte
It is assembled after the anode superposition of cladding using hot pressing mode.Hot compression parameters for example can be with are as follows: the temperature of hot pressing is 240~290
DEG C, hot pressing pressure is 5~20MPa, 0.5~2h of hot pressing time.
In hot pressing, by applying certain pressure, it can make to fit closely between positive and negative anodes, reduce positive electrode and negative electrode
And the gap between solid electrolyte.Conductive foams can be squeezed by hot pressing simultaneously, reduce the volume shared by it, into
One step reduces the volume of all-solid-state battery, improves its volume energy density.In addition, solid electrolyte is by glassy state by hot pressing
It is converted into the solid electrolyte of glass-ceramic state, improves its conductivity.In addition, by hot pressing, binder can be decomposed into bonding
The stronger small molecule of property, to keep the contact between solid electrolyte and positive electrode active materials closer.
5th aspect, the present invention provides a kind of lithium ion batteries, including cathode, anode, electrolyte and diaphragm；Wherein,
Anode includes conductive foams and is filled in the intrapore positive electrode active materials of conductive foams；
Cathode is Carbon foam, or, cathode includes conductive foams and the negative electrode active that is filled in conductive foams
Material.
Conductive foams for example can be Carbon foam or foam metal.Percent opening >=95% of conductive foams.
The lithium ion battery has beneficial effect identical with above-mentioned all-solid-state battery, and details are not described herein.
The structure of the soft bag lithium ionic cell of one embodiment of the present invention is as shown in Fig. 2, include aluminum plastic film 10 and encapsulation
In cathode 20, anode 30, electrolyte 40 and diaphragm 50 in aluminum plastic film 10；Anode includes conductive foams and is filled in conduction
Positive electrode active materials in foamed material hole；Cathode is Carbon foam.
Below in conjunction with embodiment and comparative example, the present invention is further described in detail.
Embodiment 1
The present embodiment is a kind of anode, including the Carbon foam as positive electrode active materials carrier and is filled in the Carbon foam
Positive electrode active materials.Wherein, the percent opening of Carbon foam is 99%, and positive electrode active materials are to use LiNbO3Coat LiCoO2。
Embodiment 2
The present embodiment is the preparation method for the anode that embodiment 1 provides, comprising the following steps:
A) commercial melamine foamed plastic is cut into 5cm × 5cm × 1cm shape, be put into tube furnace, N2Protect gas
The lower 800 DEG C of carbonizations 2h of atmosphere, after cooling, with washes of absolute alcohol, 60 DEG C of dryings obtain the Carbon foam of self-supporting three-dimensional structure, will
Gained Carbon foam is cut to obtain 5cm × 5cm × 0.1cm Carbon foam by required size；
B) LiNbO is provided3The LiCoO of cladding2As positive electrode active materials, by the mass ratio of 97:3 by the positive-active material
Material and polypropylene carbonate binder are dissolved in acetonitrile solution, and 50 DEG C of stirring 6h obtain positive solution, by the Carbon foam after cutting
It is soaked in the positive solution, 60 DEG C of dryings after taking-up, repeats to infiltrate dry process 3 times later, obtain anode.
Embodiment 3
The present embodiment is a kind of cathode, including the foam copper as negative electrode active material carrier and is filled in the foam copper
Negative electrode active material.Wherein, the percent opening of foam copper is 95%, and negative electrode active material is graphite.
Embodiment 4
The present embodiment is a kind of anode, including the foamed aluminium as positive electrode active materials carrier and is filled in the foamed aluminium
Positive electrode active materials.Wherein, the percent opening of foamed aluminium is 85%, and positive electrode active materials are to use LiNbO3Coat LiCoO2。
Embodiment 5
The present embodiment is a kind of all-solid lithium-ion battery, as shown in figure 3, including cathode 20, anode 30 and solid-state electricity
Matter 60 is solved, cathode 20 is Carbon foam, and the percent opening of Carbon foam is 99%, the anode that anode 30 provides for embodiment 1, solid state electrolysis
Matter 60 is coated on 20 surface of cathode.
Embodiment 6
The present embodiment is the preparation method for the all-solid lithium-ion battery that embodiment 5 provides, comprising the following steps:
A) commercial melamine foamed plastic is cut into 5cm × 5cm × 1cm shape, be put into tube furnace, N2Protect gas
The lower 800 DEG C of carbonizations 2h of atmosphere, after cooling, with washes of absolute alcohol, 60 DEG C of dryings obtain the Carbon foam of self-supporting three-dimensional structure, will
Gained Carbon foam is cut to obtain 5cm × 5cm × 0.1cm Carbon foam by required size；
B) in the argon gas filling glove box in oxygen and water content less than 0.1ppm, Li is weighed with the molar ratio of 7:32S and
P2S5It is dissolved in anhydrous acetonitrile as solid electrolyte raw material, 3wt% is then added (with Li2S and P2S5Total weight conduct
Mete-wand) binder polypropylene carbonate, 60 DEG C of stirrings for 24 hours, obtain homogeneous solution, and the Carbon foam that step a) is obtained is soaked
Enter into above-mentioned homogeneous solution, takes out and be put into clean glassware after infiltration 10mim, air drying obtains solid state electrolysis
The cathode of matter cladding；
C) LiNbO is provided3The LiCoO of cladding2As positive electrode active materials, by the mass ratio of 97:3 by the positive-active material
Material and polypropylene carbonate binder are dissolved in acetonitrile solution, and 50 DEG C of stirring 6h obtain positive solution, by the Carbon foam after cutting
It is soaked in the positive solution, air drying after taking-up, repeats to infiltrate dry process 3 times later, obtain anode；
D) in the argon gas filling glove box in oxygen and water content less than 0.1ppm, by solid electrolyte packet obtained above
The cathode and anode covered is superimposed, under 10MPa pressure, 250 DEG C of hot pressing 1h, then in positive and negative anodes pole piece edge extraction pole
Ear, last aluminum plastic film encapsulation, obtains solid lithium ion battery.
Embodiment 7
The present embodiment is a kind of all-solid lithium-ion battery, including cathode, anode and electrolyte, and cathode is embodiment 3
In cathode, the percent opening of the foam copper is 95%, and just extremely the anode that provides of embodiment 1, solid electrolyte are coated on cathode
Surface.
The preparation method of solid lithium ion battery in the embodiment the following steps are included:
A) using commercial graphite as negative electrode active material, by the mass ratio of 97:3 by the negative electrode active material and poly- carbonic acid
Acrylic ester binder is dissolved in acetonitrile solution, and 50 DEG C of stirring 6h obtain negative solution, and 5cm × 5cm × 0.1cm foam copper is impregnated
In the negative solution, air drying after taking-up repeats to infiltrate dry process 3 times later, obtains negative electrode tab；
B) in the argon gas filling glove box in oxygen and water content less than 0.1ppm, Li is weighed with the molar ratio of 7:32S and
P2S5It is dissolved in anhydrous acetonitrile as solid electrolyte raw material, 3wt% is then added (with Li2S and P2S5Total weight conduct
Mete-wand) binder polypropylene carbonate, 60 DEG C stirring for 24 hours, obtain homogeneous solution, then negative electrode tab is immersed in above-mentioned
It in homogeneous solution, takes out and is put into clean glassware after infiltration 10mim, air drying obtains solid electrolyte cladding
Cathode；
C) LiNbO is provided3The LiCoO of cladding2As positive electrode active materials, by the mass ratio of 97:3 by the positive-active material
Material and polypropylene carbonate binder are dissolved in acetonitrile solution, and 50 DEG C of stirring 6h obtain positive solution, by 5cm × 5cm × 0.1cm
Carbon foam be soaked in the positive solution, air drying after taking-up repeats to infiltrate dry process 3 times later, obtains anode；
D) in the argon gas filling glove box in oxygen and water content less than 1ppm, solid electrolyte obtained above is coated
Cathode and anode be superimposed, under 10MPa pressure, 250 DEG C of hot pressing 1h, then positive and negative anodes pole piece edge draw tab,
Last aluminum plastic film encapsulation, obtains solid lithium ion battery.
Embodiment 8
The present embodiment is a kind of all-solid lithium-ion battery, including cathode, anode and electrolyte, and cathode is Carbon foam,
The percent opening of Carbon foam is 99%, and just extremely the anode of the offer of embodiment 4, solid electrolyte are coated on negative terminal surface.
The preparation method of solid lithium ion battery in the embodiment the following steps are included:
A) 5cm × 5cm × 0.1cm Carbon foam is provided as cathode, is less than the argon gas of 0.1ppm in oxygen and water content
It fills in glove box, Li is weighed with the molar ratio of 7:32S and P2S5It is dissolved in anhydrous acetonitrile as solid electrolyte raw material,
3wt% is then added (with Li2S and P2S5Total weight as mete-wand) binder polypropylene carbonate, 60 DEG C stirring
For 24 hours, homogeneous solution is obtained, then foamed aluminium is immersed in above-mentioned homogeneous solution, taking-up is put into clean glass after infiltrating 10mim
In glass vessel, air drying obtains the cathode of solid electrolyte cladding；
B) LiNbO is provided3The LiCoO of cladding2As positive electrode active materials, by the mass ratio of 97:3 by the positive-active material
Material and polypropylene carbonate binder are dissolved in acetonitrile solution, and 50 DEG C of stirring 6h obtain positive solution, by 5cm × 5cm × 0.1cm
Foamed aluminium be soaked in the positive solution, air drying after taking-up repeats to infiltrate dry process 3 times later, obtains anode；
C) in the argon gas filling glove box in oxygen and water content less than 0.1ppm, by solid electrolyte packet obtained above
The cathode and anode covered is superimposed, under 10MPa pressure, 250 DEG C of hot pressing 1h, then in positive and negative anodes pole piece edge extraction pole
Ear, last aluminum plastic film encapsulation, obtains solid lithium ion battery.
Comparative example 1
This comparative example is a kind of lithium ion solid state battery, including the cathode, solid electrolyte and anode set gradually,
In, cathode is copper foil and the graphite linings coated on copper foil surface, just extremely aluminium foil and the positive electrode material layer coated on aluminium foil surface
(positive electrode active materials and binder that the positive electrode material layer includes the identical proportion in embodiment 6), in the positive electrode material layer
Material composition is identical as the composition of positive electrode in embodiment 6.Meanwhile in the comparative example lithium ion solid state battery positive and negative anodes
Also identical (wherein, the overall thickness of the copper foil in the comparative example and graphite linings and foam in embodiment 6 in size and embodiment 6
The thickness of charcoal is identical, and the overall thickness of copper foil and positive electrode material layer is identical as thickness positive in embodiment 6).In the comparative example
The assemble method of lithium ion solid state battery be it is conventional be coated and dried, lamination and plastic package process.
The mass energy density and volume energy for the lithium ion solid state battery that testing example 6-8 and comparative example 1 provide respectively
Metric density, test result are listed in table 1.
1 test result of table
It can be seen that the present invention from the data in table 1 and the mass energy density and volume energy of lithium ion solid state battery be provided
Metric density is all larger than the lithium ion solid state battery in comparative example 1.
To sum up, lithium ion solid state battery provided by the invention has the advantage that
1) secondary cell provided by the invention has carried out process modification to existing battery structure, after improvement, eliminates afflux
The use of body reduces the space waste of inside battery, improves the volume energy density of battery；
2) relative to traditional solid state battery, battery structure proposed by the present invention saves copper foil, aluminium foil, binder
It uses, to improve the mass energy density of battery；
3) concept of the conductive foams of three-dimensional net structure proposed by the present invention has relative to traditional structure battery
Incomparable advantage is expected to lead the trend of next-generation rechargeable battery structure design.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of electrode, which is characterized in that the electrode includes the conductive foams as support body framework and is filled in institute
State the intrapore electrode active material of conductive foams；Wherein, the electrode active material is positive electrode active materials or cathode
Active material.
2. electrode according to claim 1, which is characterized in that the conductive foams are Carbon foam or foam metal；
Preferably, percent opening >=95% of the conductive foams.
3. a kind of preparation method of electrode, which is characterized in that by the conductive foams as support body framework be soaked in containing
In the solution of electrode active material, electrode is obtained after drying；Wherein, the electrode active material is positive electrode active materials or bears
Pole active material.
4. preparation method according to claim 3, which is characterized in that the foam conductive material is Carbon foam or foam gold
Belong to.
5. the preparation method according to claim 4, which is characterized in that the Carbon foam is will have the polymerization of foaming structure
Object obtains after carrying out carbonization treatment；
Preferably, the polymer is melamine or melamine derivative；Wherein, carburizing temperature is 600~900 DEG C, carbon
The change time is 1~6h.
6. a kind of all-solid-state battery, which is characterized in that including cathode, anode and electrolyte；Wherein,
The anode includes conductive foams and is filled in the intrapore positive electrode active materials of the conductive foams；
The cathode is Carbon foam, or, the cathode includes conductive foams and is filled in the conductive foams hole
Interior negative electrode active material.
7. all-solid-state battery according to claim 6, which is characterized in that the solid electrolyte is coated on the positive table
Face and/or the negative terminal surface；
Preferably, the conductive foams are Carbon foam or foam metal；
Preferably, percent opening >=95% of the conductive foams.
8. a kind of preparation method of all-solid-state battery, which is characterized in that comprising steps of
Step S1: conductive foams are soaked in the solution containing negative electrode active material, cathode are obtained after dry, or directly
Using Carbon foam as cathode；
Step S2: conductive foams are soaked in the solution containing positive electrode active materials, obtain anode after dry；
Step S3: anode and/or cathode are soaked in the solution containing solid electrolyte and binder, complete electrode after dry
Electrolyte cladding；
Step S4: it will be assembled after anode and cathode superposition using hot pressing mode, wherein temperature is 240~290 DEG C, pressure
For 5~20MPa, the time is 0.5~2h.
9. preparation method according to claim 8, which is characterized in that the conductive foams are Carbon foam or foam gold
Belong to；
Preferably, percent opening >=95% of the conductive foams.
10. a kind of lithium ion battery characterized by comprising cathode, anode, electrolyte and diaphragm；Wherein,
The anode includes conductive foams and is filled in the intrapore positive electrode active materials of the conductive foams；
The cathode is Carbon foam, or, the cathode includes conductive foams and is filled in the conductive foams
Negative electrode active material；
Preferably, the conductive foams are Carbon foam or foam metal；
Preferably, percent opening >=95% of the conductive foams.
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| CN110112457A (en) * | 2019-05-23 | 2019-08-09 | 桑德新能源技术开发有限公司 | A kind of all-solid-state battery and preparation method thereof |
| CN111864276A (en) * | 2019-04-26 | 2020-10-30 | 本田技研工业株式会社 | Method for manufacturing solid-state battery and solid-state battery |
| CN111969252A (en) * | 2020-08-31 | 2020-11-20 | 蜂巢能源科技有限公司 | Solid-state battery and method for manufacturing same |
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