CN108899472A - A kind of lithium metal battery electrode slice and preparation method thereof and a kind of lithium metal battery - Google Patents
A kind of lithium metal battery electrode slice and preparation method thereof and a kind of lithium metal battery Download PDFInfo
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- CN108899472A CN108899472A CN201810813168.2A CN201810813168A CN108899472A CN 108899472 A CN108899472 A CN 108899472A CN 201810813168 A CN201810813168 A CN 201810813168A CN 108899472 A CN108899472 A CN 108899472A
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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
- 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
- H01M4/139—Processes of manufacture
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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 lithium metal battery cathode pole pieces, are suppressed by metal lithium sheet and sponge.When cathode pole piece provided by the invention is applied in lithium metal battery, it can simplify traditional lithium metal battery structure, introducing sponge elastic interface layer replaces diaphragm to play electronics barrier action, and this elastic interface material is introduced into the Rayleigh Taylor that can alleviate volume change and inside battery in circulating battery.And sponge medium layer and the wellability of electrolyte are very good, stronger compared to common polypropylene diaphragm (Polypropylene) thermal deformation resistant ability.The resilient three-dimensional skeleton structure of sponge is conducive to inhibit the dendritic growth in lithium metal battery cyclic process simultaneously；It is also beneficial to alleviate the volume change of cathode.Therefore, this further development that can push lithium metal battery from another angle without membrane configuration composition metal cathode of lithium designed using sponge material.
Description
Technical field
The invention belongs to lithium metal battery technical fields, and in particular to a kind of lithium metal battery electrode slice and its preparation side
Method and a kind of lithium metal battery.
Background technique
On the one hand, due to having current highest theoretical capacity (3860mA h g-1), minimum electrochemical potential (-
3.04V), lower density (0.534g cm-3) etc. advantages, lithium anode be deemed likely to be next-generation energy storage system hair
Open up direction.On the other hand, with the exploitation of next-generation high energy battery system, such as：The research of lithium sky battery and lithium-sulfur cell
And development, the application study of lithium metal battery also highlight its importance.However, since there are high activities and lithium for lithium metal itself
The problem of dendrite, is not solved, and safety and cyclicity limit commercial applications.Wherein：(1) it is examined from the angle of safety
Consider, the constantly lower Li dendrite grown of circulation is easy to pierce through battery diaphragm, then causes battery plus-negative plate short-circuit, generates the things such as on fire
Therefore hidden danger.(2) consider from the structure of full battery, the lithium metal of cathode can bring the volume of no host's property to become with charge and discharge degree
Change, calculates and know：Theoretically, when circulating battery face amount reaches 10mAh/cm2When, the lithium Interface Moving in full battery will reach
50 μm, then generate biggish internal stress.(3) consider from negative electrode interface, firstly, cathode is initial with electrolyte interface
The dendrite protrusion of generation causes partial charge and is unevenly distributed, and accelerates lithium dendrite growth；Secondly, the generation of cathode Li dendrite makes
It obtains lithium metal surface in cyclic process and constantly regenerates solid electrolyte interface film (Solid Electrolyte
Interface, SEI), this affects the coulombic efficiency of battery.
On the other hand, in traditional lithium ion battery at present, diaphragm be in the big main material of battery four technical barrier and
The highest material of rate of gross profit.Normally, the diaphragm in battery component is by apertured polymeric film, glass fibre membrane or porous ceramic film
It is made, plays barrier electronics, the effect for allowing ion to pass through.Such as：China Patent Publication No. is that CN106252568 discloses one
Lithium ion battery separator kind resistant to high temperature and preparation method, and for novel lithium metal battery, the research in terms of diaphragm is opposite
It is less, using it is more be still for polypropylene screen (Polypropylene), the glass fibre membrane in conventional lithium ion battery
(Glass Fiber) and polypropylene-polyethylene-polypropylene composite film (Polypropylene-Polyethylene-
Polypropylene).But above-mentioned diaphragm thermal deformation resistant ability is poor, so that the probability of lithium battery positive and negative electrode contact can be increased.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of lithium metal battery cathode pole piece, this hair
When the lithium metal battery of bright offer is applied in lithium metal battery with cathode pole piece, membrane configuration can be saved, in cathode pole piece
Spongiotic elastic interface can alleviate the Rayleigh Taylor of volume change and inside battery in circulating battery.
The present invention provides a kind of lithium metal battery cathode pole pieces, which is characterized in that by metal lithium sheet and sponge pressure
It makes.
Preferably, the metal lithium sheet with a thickness of 50~1000 μm, the sponge with a thickness of 1~5mm, the cathode
Pole piece with a thickness of 800~6000 μm.
Preferably, the density of the sponge is about 0.01~0.02g/cm3, porosity is up to 98%~99%, aperture 50
~100 μm.
Preferably, the sponge is selected from one of polyurethane sponge, cellular rubber and melamine sponge or a variety of.
The present invention also provides a kind of preparation methods of lithium metal battery cathode pole piece, include the following steps：
Under the conditions of protective atmosphere, application physical pressure is compound with lithium piece by sponge, obtains cathode pole piece.
Preferably, the protective atmosphere condition is selected from argon atmosphere, and the water oxygen content in the protective atmosphere is respectively less than
0.1ppm。
The present invention also provides a kind of lithium metal batteries, including anode, cathode and electrolyte, and do not include diaphragm, described
Cathode is selected from above-mentioned cathode pole piece.
Preferably, the electrolyte is selected from lithium-ion battery electrolytes or lithium-sulfur cell electrolyte.
Preferably, the positive electrode of the anode is selected from sulphur and traditional embedded type positive electrode：Li4Ti5O12、
LiFePO4、LiCoO2Middle one or more.
Compared with prior art, the present invention provides a kind of lithium metal battery cathode pole pieces, by metal lithium sheet and sea
Silk floss is suppressed.When cathode pole piece provided by the invention is applied in lithium metal battery, traditional lithium metal battery can simplify
Structure introduces sponge elastic interface layer and diaphragm is replaced to play electronics barrier action, and the introducing of this elastic interface material can be with
Alleviate the Rayleigh Taylor of volume change and inside battery in circulating battery.And the leaching of sponge medium layer and electrolyte
Lubricant nature is very good, stronger compared to common polypropylene diaphragm (Polypropylene) thermal deformation resistant ability.The elasticity of sponge simultaneously
Three dimensional skeletal structure is conducive to inhibit the dendritic growth in lithium metal battery cyclic process；The volume for being also beneficial to alleviate cathode becomes
Change.Therefore, this to push lithium from another angle without membrane configuration composition metal cathode of lithium using what sponge material designed
The further development of metal battery.
The result shows that the half-cell that lithium metal battery provided by the invention is assembled with cathode pole piece is conventionally surveyed
Examination coulombic efficiency can reach 98% by average value after 63 circles.It is symmetrically electric to test lithium metal of the sponge composite material without membrane configuration
Pond cycle performance obtains：In high current density (10mA cm-2) and large capacity (10mAhcm-2) under also show it is lower excessively electric
Gesture and stablize circulation 200 hours；In 1mA cm-2Smaller current density and 1mAhcm-2It is equally also shown under capacity lower
Overpotential and circulation can be stablized.
Detailed description of the invention
Fig. 1 is the optical microphotograph picture (left side) and SEM picture for the sponge material selected in the embodiment of the present invention 1,2
(right side)；
Fig. 2 is that the sponge material selected in the embodiment of the present invention 1,2 and polypropylene diaphragm keep the number before 1h at 150 DEG C
Code photo comparison；
Fig. 3 is the office at sponge in the embodiment of the present invention 1,2, lithium metal composite material SEM front elevation, sectional view and compound place
Portion's figure；
Pair that the sponge of Fig. 4 embodiment of the present invention 1 and the preparation of comparative example 1, lithium metal combination electrode are designed without membrane configuration
Claim the loop test figure of battery and the loop test comparison diagram of lithium metal Symmetrical cells；
Fig. 5 is by testing the sponge that coulombic efficiency assembles, lithium metal combination electrode without membrane configuration in the embodiment of the present invention 2
Lithium metal battery (the model of design：CR2032) structural schematic diagram；
Fig. 6 is the sponge of the embodiment of the present invention 2 and the preparation of comparative example 2, lithium metal combination electrode is designed without membrane configuration
The coulombic efficiency test comparison chart of lithium metal half-cell；
Fig. 7 be different-thickness described in embodiment 3 in the present invention sponge elastic interface layer assemble half-cell circulation and
Coulombic efficiency test comparison chart；
First three the circle loop test for the full battery that Fig. 8 assembles for sponge elastic interface layer as described in example 4 in the present invention
Figure and coulombic efficiency test chart.
Specific embodiment
The present invention provides a kind of lithium metal battery cathode pole pieces, are suppressed by metal lithium sheet and sponge.
Wherein, the metal lithium sheet with a thickness of 50~1000 μm, preferably 200~800 μm, further preferably 300
~600 μm, further preferably 0.4~0.5mm, most preferably 0.46mm.
The diameter of the metal lithium sheet is preferably 12~16mm, more preferably 14mm.
In the present invention, the lithium metal piece is preferably that this field prepares the normal of lithium ion battery half-cell negative electrode material
Advise round lithium piece.The lithium metal piece may be other shapes, have no specifically limited.
The sponge with a thickness of 1~5mm, preferably 2~4mm, further preferably 2.5~3mm.
Formed the cathode pole piece with a thickness of 800~6000 μm, preferably 1500~2900 μm.The electrode slice is
When round, the diameter of the electrode slice is preferably 5~16mm, more preferably 10mm.
In the present invention, the density of the sponge is about 0.01~0.02g/cm3, porosity is up to 98%~99%, aperture
It is 50~100 μm, preferably 60~90 μm, further preferably 70~80 μm.
The sponge is selected from one of polyurethane sponge, cellular rubber and melamine sponge or a variety of.
In the present invention, the lithium metal battery is suppressed with cathode pole piece by metal lithium sheet and sponge.Wherein, by
Soft in lithium metal, by the two pressing process, the lithium of the one side contacted with sponge can be embedded in since pressure generates deformation
Into the hole of sponge, therefore lithium layer-lithium/sponge transition layer-spongy layer composite construction can be generated.Wherein, the lithium/sponge
When transition zone is that metal lithium sheet is suppressed with sponge, lithium is embedded in the transition layer structure formed in the hole of sponge.
The present invention also provides a kind of preparation methods of lithium metal battery cathode pole piece, include the following steps：
Under the conditions of protective atmosphere, application physical pressure is compound with lithium piece by sponge, obtains cathode pole piece.
Firstly, sponge is cut to required thickness, then it is cut, obtains the sponge sheet of certain size；
Then sponge sheet is superimposed with lithium piece, under the conditions of protective atmosphere, applies physical pressure, obtain composite sheet；
Wherein, the protective atmosphere condition is selected from argon atmosphere, and the water oxygen content in the protective atmosphere is respectively less than
0.1ppm.In the present invention, the pressing process of sponge sheet and lithium piece carries out preferably in glove box.Present invention preferably employs hydraulic
Sealing machine applies physical pressure.
Finally, obtained composite sheet is cut, the cathode pole piece of required size is obtained.
The present invention to the shape of the cathode pole piece and size there is no specifically limited, well known to a person skilled in the art
It can be used for the shape and size of the cathode pole piece of lithium metal battery.
The structure design on the one hand take full advantage of sponge material three-dimensional structure and can receiving volume variation elasticity,
On the other hand, the physical barrier of spongy layer is also utilized, the barrier electronics similar to presently used diaphragm, conducting ion have been played
Effect.Whole preparation process is simple, can mass production.
The lithium metal half-cell and Symmetrical cells assembled by above-mentioned cathode pole piece is shown under different current densities
The coulombic efficiency and superior cycle performance more more stable than lithium metal.Wherein the half-cell of cathode pole piece assembling is according to routine
Method test coulombic efficiency can reach 98% by average value after 63 circles, and test result is substantially better than under the same terms by lithium metal
The control cell of piece and polypropylene diaphragm (Polypropylene) assembling.Test what cathode pole piece provided by the present invention obtained
The lithium metal Symmetrical cells cycle performance of no membrane configuration obtains：In high current density (10mA cm-2) and large capacity
(10mAhcm-2) under also show lower overpotential and stablize circulation 200 hours；In 1mA cm-2Smaller current density and
1mAhcm-2Lower overpotential is equally also shown under capacity and can stablize circulation.
Wherein, half-cell structure successively includes by negative electrode casing to anode cover：Negative electrode casing, lithium piece-sponge, electrolyte, copper sheet,
Gasket, elastic slice, anode cover.
Symmetrical cells structure successively includes by negative electrode casing to anode cover：Negative electrode casing；Lithium piece-sponge-lithium piece；Gasket, elastic slice
And anode cover.
The present invention also provides a kind of lithium metal batteries, including anode, cathode and electrolyte, and do not include diaphragm, described
Cathode is selected from above-mentioned lithium metal battery cathode pole piece.
Wherein, the present invention to the type of the electrolyte there is no specifically limited, well known to a person skilled in the art lithium from
Sub- battery electrolyte or lithium-sulfur cell electrolyte.Preferably, the lithium-sulfur cell electrolyte can be selected from 1M LiTFSI
(DOL:DME=1:1vol%)+2wt%LiNO3The electrolyte of formation,
Specially：With volume ratio for 1:1 DOL and DME is 1M in concentration wherein as mixed solvent, LiTFSI, then
2wt%LiNO is added thereto3The electrolyte of formation.
Lithium-ion electrolyte can be selected from 1M LiF6(EC:DEC=1:Electrolyte 1vol%), specially with volume ratio
It is 1:1 EC and DEC is as mixed solvent, LiF6It is 1M in concentration wherein.
The present invention is not specifically limited to the anode of the lithium metal battery, and well known to a person skilled in the art anodes to be
Can, the type of the positive electrode is also not particularly limited, well known to a person skilled in the art positive electrodes.
In the present invention, the positive electrode is selected from sulphur and traditional embedded type anode：Li4Ti5O12、LiFePO4、
LiCoO2Middle one or more.
The assembling process of the battery carries out preferably in the glove box with inert atmosphere conditions.Then this field is used
Conventional battery encapsulation method obtains the lithium metal Symmetrical cells of button-shaped no membrane configuration and tests half electricity of coulombic efficiency
Pond.
Referring to Figure 5, the structure of the half-cell includes：Negative electrode casing, lithium piece, sponge, electrolyte, lithium piece/copper foil, pad
The sequence of piece, elastic slice and anode cover assembles.
In this certain specific embodiments of the invention, the structure of the lithium metal full battery includes：Using the lithium of LTO
Metal full battery may be designed as without membrane configuration：Negative electrode casing, above-mentioned cathode pole piece, electrolyte, LTO, gasket, elastic slice, anode cover.
The preparation method simple process of cathode pole piece provided by the invention, cost is relatively low, and obtain without membrane configuration
Lithium metal battery better performances.
The present invention provides a kind of lithium metal battery of novel no membrane configuration, the sea being prepared by pressure bonding
The stable circulation that continuous, Symmetrical cells of the lithium metal without membrane configuration can be maintained for a long time under the different current densities of setting
Property.
The present invention also provides the big electricity of lithium metal half-cell and Symmetrical cells that sponge, lithium metal are assembled without membrane configuration
As a result, simultaneously comparing with simple lithium metal Symmetrical cells, novel no diaphragm system is shown more current density loop test
Excellent cyclical stability.
Wherein, Symmetrical cells test method is：The button cell that above-mentioned assembling is obtained is after standing 12h, first to set
Current density discharge 1h, then with identical current density charge 1h, and constantly reignition charging process, until battery
Stop experiment when overpotential increased dramatically or drastically reduce, illustrates battery open circuit or short circuit.It can be visited using this test method
Study carefully the sponge of use, lithium metal composite material under the current density of setting the cyclical stability of lithium deposition and precipitation process and
It inhibits the effect of metal Li dendrite.
Test half-cell coulombic efficiency method be：After the lithium metal button cell of assembling is stood 12h, first to set
Current density electric discharge 1h resets and charges to 1V cut-off with identical current density, and charge appearance during calculating charge and discharge cycles
Amount accounts for the ratio of discharge capacity, assessed by this ratio value battery system capacity attenuation speed and circulating battery it is reversible
Property.
The present invention is while making full use of sponge resilient three-dimensional skeleton structure, including sponge elastic interface layer is in battery
The alleviation of portion's unstability and volume change, while the physical barrier effect of sponge has been played, and lithium metal before can be replaced
Common polypropylene diaphragm (Polypropylene) or fibreglass diaphragm (Glass Fiber) in battery, formed novel nothing every
Film negative pole structure.Whole preparation process is not only simple and easy, and the lithium metal battery save the cost of this novel no membrane configuration,
Be conducive to its large-scale application development.
For a further understanding of the present invention, below with reference to embodiment to lithium metal battery electrode slice provided by the invention and
Preparation method and lithium metal battery are illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Lithium metal battery preparation that melamine sponge, lithium metal composite elastic boundary material are designed without membrane configuration and right
Claim circulating battery test：
The sponge material of ready cleaning is cut into the thickness of 2.5mm with scalpel；It reuses formed punch and determines diameter
For the sponge disk of 16mm；Wherein, the density of sponge is 0.01~0.02g/cm3, porosity is 98%~99%, aperture 50
~100 μm.Referring to Fig. 1, Fig. 1 is the optical microphotograph picture (left side) and SEM for the sponge material selected in the embodiment of the present invention 1,2
Picture (right side).
The sponge material is placed at 150 DEG C and keeps 1h, and by before and after it state and size take pictures, as a result
See that Fig. 2, Fig. 2 are that the sponge material selected in the embodiment of the present invention 1,2 and polypropylene diaphragm keep the number before 1h at 150 DEG C
Photo comparison.In Fig. 2, left figure is that the sponge material selected and polypropylene diaphragm be before heat treatment in the embodiment of the present invention 1,2
The digital photograph of state, right figure are that the sponge material selected in the embodiment of the present invention 1,2 and polypropylene diaphragm are kept at 150 DEG C
The digital photograph of state after 1h.As seen from Figure 2, after keeping 1h at 150 DEG C, the sponge selected in embodiment 1,2
Scantling changes there is no apparent, but the size of polypropylene diaphragm but significantly shrinks and becomes smaller.
Prepare metal lithium sheet, with a thickness of 450 μm.After above-mentioned sponge material is superimposed with metal lithium sheet, in argon gas glove box
It is middle to apply physical pressure using small-sized hydraulic sealing machine, obtain the sponge with a thickness of 800~1200 μm-lithium piece cathode pole piece.
To the sponge-lithium piece cathode pole piece be scanned Electronic Speculum observation, the result is shown in Figure 1, Fig. 1 be the embodiment of the present invention 1,
Sponge in 2, lithium metal composite material SEM front elevation (on), sectional view (in) and compound place Local map (under).By compound
As can be seen that the lithium of the one side contacted with sponge can be embedded into the hole of sponge since pressure generates deformation in Local map.
Then it is designed in glove box according to novel no membrane configuration：Negative electrode casing, lithium piece, electrolyte, above-mentioned sponge-lithium
Piece cathode pole piece, gasket, elastic slice, anode cover are assembled into lithium metal battery.Finally electricity is encapsulated according to conventional hydraulic encapsulation technology
Pond.The selected lithium metal piece of experiment is gone out using the formed punch that diameter is 10mm, and electrolyte uses：1M LiTFSI(DOL:
DME=1:1vol%)+2wt%LiNO3Electrolyte, the operation carry out in argon gas glove box, and wherein water oxygen content is equal
Less than 0.1ppm.
Battery is tested using conventional blue electrical testing channel, first with the current density constant current discharge 1h of setting when test,
Again with identical current density charging 1h, and this charge and discharge cycles is constantly repeated, is provided with two kinds of current densities of size：
10mA/cm2；1mA/cm2.Stability and the sea of circulating battery process are judged by the variation of observation potential and circulation time
Inhibiting effect of the continuous compound system to Li dendrite.
Referring to fig. 4, Fig. 4 is the sponge of the embodiment of the present invention 1 and the preparation of comparative example 1, lithium metal combination electrode without diaphragm knot
The loop test figure of the Symmetrical cells of structure design and the loop test comparison diagram of lithium metal Symmetrical cells.As shown in Figure 4, in big electricity
Current density：10mA/cm2Under, sponge shows more stable potential with circulation time without the Symmetrical cells that membrane configuration designs and becomes
Change；Similarly, in low current density 1mA/cm2Under lower, more stable potential change is also shown with circulation time.It illustrates
The elastic interface layer and its three-dimensional structure of sponge medium are more advantageous to compared to conventional lithium ion battery diaphragm improves the heavy of lithium metal
Cyclical stability in product, stripping process.
Comparative example 1
Assembling and Symmetrical cells loop test pair of the polypropylene diaphragm (Polypropylene) for conventional lithium metal battery
Than experiment：
Using traditional lithium metal battery structure：Negative electrode casing, lithium piece, PP diaphragm, electrolyte, lithium piece, gasket, elastic slice, just
Pole shell is assembled into lithium metal Symmetrical cells, then encapsulates battery according to conventional hydraulic encapsulation technology.The selected lithium gold of experiment
Category piece is same as Example 1 and is gone out using the formed punch that diameter is 10mm, and electrolyte, which uses, is：1M LiTFSI(DOL:
DME=1:1vol%)+2wt%LiNO3, the operation carries out in argon gas glove box, the method for test half-cell circulation
It is same as Example 1 with condition.
Embodiment 2
Sponge, lithium metal composite elastic boundary material is prepared without the lithium metal battery that membrane configuration designs and half-cell coulomb
The test of efficiency：
Combined electrode is prepared with a thickness of the sponge of 2.5mm using prepared by embodiment 1, is designed by no membrane configuration
It is assembled into novel lithium metal battery.Unlike the first embodiment：Test battery structure used by half-cell coulombic efficiency
For：Negative electrode casing, lithium piece-sponge, electrolyte, copper sheet, gasket, elastic slice, anode cover.It is in the embodiment of the present invention 2 referring to Fig. 5, Fig. 5
Lithium metal battery (the model that the sponge that is assembled of test coulombic efficiency, lithium metal combination electrode are designed without membrane configuration：
CR2032) structural schematic diagram.
The selected lithium metal piece of experiment and copper sheet are gone out using the formed punch of diameter 10mm, and electrolyte, which uses, is：
1M LiTFSI(DOL:DME=1:1vol%)+2wt%LiNO3；The operation carries out in glove box.
The coulombic efficiency of half-cell is tested using conventional blue electrical measurement test system, is specifically included：By the lithium metal knob of assembling
After detaining battery standing 12h, the first current density 1mA/cm to set2Discharge 1h, resets and is charged to identical current density
1V ends, and charging capacity accounts for the ratio of discharge capacity, the pass that this ratio value changes over time during calculating charge and discharge cycles
System is used to the speed of assessment battery capacity decaying.As a result see that Fig. 6, Fig. 6 are the embodiment of the present invention 2 and sea prepared by comparative example 2
The coulombic efficiency test comparison chart for the lithium metal half-cell that continuous, lithium metal combination electrode is designed without membrane configuration.
It will be appreciated from fig. 6 that the elastic interface layer that sponge is designed without membrane configuration is compared to polypropylene diaphragm
(Polypropylene) higher initial coulombic efficiency value and average coulombic efficiency value, this explanation are shown in cyclic process
Sponge elastic interface layer and its three-dimensional structure have in lithium metal battery cyclic process less compared to traditional polypropylene diaphragm
Lithium loss and " dead lithium " formed, to possess higher lithium metal utilization rate in cyclic process.
Comparative example 2
Assembling and half-cell coulombic efficiency test of the polypropylene diaphragm (Polypropylene) for conventional lithium metal battery
Comparative experiments：
Using traditional lithium metal structure：Negative electrode casing, lithium piece, polypropylene diaphragm, copper sheet, gasket, elastic slice, anode cover group
Dress, it is hydraulic to be packaged into lithium metal battery.The selected lithium metal piece of experiment and copper sheet are gone out using the formed punch of diameter 10mm, electricity
Solution liquid, which uses, is：1MLiTFSI(DOL:DME=1:1vol%)+2wt%LiNO3, operating process is similar to Example 2,
The condition for testing half-cell coulombic efficiency is same as Example 2.
As seen from the above embodiment, the present invention provides a kind of lithium metal battery of novel no membrane configuration and sponges, gold
Belong to lithium combination electrode material, it is described.The present invention also provides a kind of electrode slice and lithium metal batteries.It is logical that the present invention provides electrode slice
It crosses no membrane configuration and designs the lithium metal battery being prepared, this lithium metal battery has good cyclical stability and higher
Coulombic efficiency.Moreover, the preparation process of sponge provided by the invention, lithium metal composite material is simple, it is suitble to large-scale industry
Metaplasia produces.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to consistent with principles disclosed herein and novelty
Widest scope.
Embodiment 3
The lithium metal half-cell preparation that the sponge of different-thickness, lithium metal composite elastic boundary material are designed without membrane configuration
And performance test：
It is adopted respectively under the same conditions to probe into influence of the sponge elastic interface layer of different-thickness to battery performance
It is assembled into half-cell with the sponge material for compressing preceding 1mm thickness and the preceding 4.5mm thickness of compression, it is similar according to embodiment 1,2
Method, the coulombic efficiency for the battery that different-thickness sponge is assembled when testing two kinds respectively under the current density of setting
And cycle performance.
Fig. 7 be different-thickness described in embodiment 3 in the present invention sponge elastic interface layer assemble half-cell circulation and
Coulombic efficiency test comparison chart.Wherein left figure is shown：Color is that the sponge that black curve is original depth 2.5mm is assembled into
The loop test of half-cell is as a result, the most shallow loop test result for relatively small thickness 1mm；And intermediate electric potential value and fluctuation are larger
Curve be original depth 4.5mm test result.As shown in Figure 7, initial thick in the sponge material of three kinds of thickness of selection
Degree is that the sponge of 2.5mm shows optimal, most stable of cycle performance, has effectively played the effect of sponge elasticity medium layer.
And the sponge material of relatively small thickness 1mm is assembled into lithium metal half-cell and the change dramatically of potential just occurs in 40 circle left and right, it may
It is since the Li dendrite of formation wears out fluctuation caused by sponge medium layer.It is then showed with a thickness of the sponge elasticity medium layer of 4.5mm
Considerably higher potential and circulation later period fluctuate situation and become apparent from out, this may be since blocked up sponge medium layer increases lithium
The internal resistance of Metal Half Cells, and reaction interface generates caused by unstable variation.
Embodiment 4
The preparation of lithium metal full battery and performance survey that sponge, lithium metal composite elastic boundary material are designed without membrane configuration
Examination：
In order to verify the exploitativeness of the sponge, lithium metal composite elastic boundary material, commercialization at present is selected
LiFePO4Full battery is assembled for positive electrode to be tested；Preparation process includes according to LiFePO4:PVDF:Conductive agent=8:
1:Positive electrode is coated on aluminium foil by 1 ratio, is weighed after dry punching, the load capacity for calculating active material is：2.0±
0.25mg/cm2。
Assembling process is similar to Example 2, and difference is to replace with copper foil into the aluminium foil coated with positive electrode.Test is adopted
With blue electrical measurement test system, specifically include：First by the static 12h of assembled battery, first with the multiplying power discharging of 0.5C to 2V, then with same
The multiplying power of sample charges to 3.8V；This process of repetitive cycling, observation capacity attenuation, the cycle performance for testing battery.
First three the circle loop test for the full battery that Fig. 8 assembles for sponge elastic interface layer as described in example 4 in the present invention
Figure and coulombic efficiency test chart.As shown in Figure 8, the specific volume of the full battery first circle assembled with sponge elasticity medium layer and metal lithium sheet
Amount is 125mAh/g (according to LiFePO4Mass Calculation), and recycle the average coulombic efficiency after 72 circles up to 96.1%；Confirm it
Has application potential.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of lithium metal battery cathode pole piece, which is characterized in that suppressed by metal lithium sheet and sponge.
2. cathode pole piece according to claim 1, which is characterized in that the metal lithium sheet with a thickness of 50~1000 μm,
The sponge with a thickness of 1~5mm, the cathode pole piece with a thickness of 800~6000 μm.
3. cathode pole piece according to claim 1, which is characterized in that the density of the sponge is 0.01~0.02g/cm3,
Porosity is 98%~99%, and aperture is 50~100 μm.
4. cathode pole piece according to claim 1, which is characterized in that the sponge is selected from polyurethane sponge, cellular rubber
With one of melamine sponge or a variety of.
5. a kind of preparation method of lithium metal battery cathode pole piece, which is characterized in that include the following steps：
Under the conditions of protective atmosphere, application physical pressure is compound with lithium piece by sponge, obtains cathode pole piece.
6. preparation method according to claim 5, which is characterized in that the protective atmosphere condition is selected from argon atmosphere, institute
The water oxygen content stated in protective atmosphere is respectively less than 0.1ppm.
7. a kind of lithium metal battery, which is characterized in that it including anode, cathode and electrolyte, and does not include diaphragm, the cathode choosing
From cathode pole piece described in Claims 1 to 4 any one.
8. lithium metal battery according to claim 7, which is characterized in that the electrolyte is selected from lithium-ion battery electrolytes
Or lithium-sulfur cell electrolyte.
9. lithium metal battery according to claim 7, which is characterized in that the positive electrode of the anode is selected from sulphur and biography
System embedded type positive electrode：Li4Ti5O12、LiFePO4、LiCoO2Middle one or more.
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