CN110112392A - Metal lithium sheet and preparation method thereof and energy storage device - Google Patents
Metal lithium sheet and preparation method thereof and energy storage device Download PDFInfo
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- CN110112392A CN110112392A CN201910410946.8A CN201910410946A CN110112392A CN 110112392 A CN110112392 A CN 110112392A CN 201910410946 A CN201910410946 A CN 201910410946A CN 110112392 A CN110112392 A CN 110112392A
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- lithium
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- decorative layer
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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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 relates to a kind of metal lithium sheets and preparation method thereof, and lithium substrate is contacted with reaction solution, carry out solid-liquid phase reaction, lithium salts decorative layer is formed on an at least side surface for lithium substrate, reaction condition is mild, and process conditions are easy, it is easily operated, it is reproducible, suitable for commercially producing on a large scale.Lithium salts decorative layer is the form compact and stable protective layer formed in lithium substrate surface, so that lithium metal uniform deposition, effectively inhibits the growth of Li dendrite.The protective layer can effectively reduce the generation of side reaction, the decomposition and consumption for reducing electrolyte, the rupture repeatedly and formation for inhibiting SEI film in charge and discharge process simultaneously, can effectively promote the cycle life and security performance of energy storage device.
Description
Technical field
The present invention relates to electrode material manufacturing fields more particularly to a kind of metal lithium sheet and preparation method thereof and energy storage to fill
It sets.
Background technique
With the development of science and technology it is intelligent, automation equipment is more more and more universal, the exploitation of these equipment is dynamic to providing for it
The requirement of the energy storage device of power is higher and higher.Under the premise of using safe, the energy storage dress of high-energy density, excellent cycle performance
Intelligent, automation equipment development can effectively be pushed by setting.
Lithium anode is because having high theoretical specific capacity (3860mAhg-1) and low reduction potential (hydrogen electrode current potential ,-
It 3.04V) is considered as a kind of negative electrode material with development potential.However, lithium metal reactivity is high, as negative electrode material
In use, lithium metal can be reacted with electrolyte, boundary layer in uneven thickness is formed at electrode/electrolyte interface, hinder lithium from
The conduction of son, causes the growth of Li dendrite and the dusting of electrode, and then causes capacity that irreversible loss occurs.On the other hand,
Lithium metal is as negative electrode material due to non-uniform deposition Li dendrite easy to form, the life of Li dendrite during charge and discharge cycles
Length can puncture diaphragm, lead to energy storage device internal short-circuit, or even cause the safety problem of thermal runaway.These problems seriously constrain
The popularization of lithium anode material largely limits application of the lithium anode material in energy storage device.
Therefore modification is carried out to lithium metal, reduces the reactivity of lithium metal, improves the stability of lithium metal, inhibits
The growth of Li dendrite, the generation for inhibiting side reaction, to the popularization of lithium anode material, improve energy storage device cycle life and
Security performance is of great significance.
Summary of the invention
Based on this, it is necessary to provide a kind of metal lithium sheet that performance is stable and preparation method thereof and energy storage device.
A kind of metal lithium sheet, including lithium substrate and lithium salts decorative layer, the lithium salts decorative layer are set to the lithium substrate extremely
On a few side surface；The lithium salts decorative layer with a thickness of 0.5 μm~20 μm.
The lithium substrate is lithium piece, lithium band or lithium foil in one of the embodiments,.
A kind of preparation method of metal lithium sheet, includes the following steps:
Under protective gas atmosphere, an at least side surface for lithium substrate is contacted with reaction solution, is existed by solid-liquid phase reaction
Lithium salts decorative layer is formed on the respective surfaces of the lithium substrate, obtains the metal lithium sheet comprising lithium substrate and lithium salts decorative layer；
The reaction solution is that lithium salts is dissolved in mixed liquor obtained in solvent.
The mass percent of the lithium salts in the reaction solution is 1%~25% in one of the embodiments,.
The lithium salts is the double oxalic acid lithium phosphates of difluoro, LiBF4, dioxalic acid boric acid in one of the embodiments,
At least one in lithium, difluorine oxalic acid boracic acid lithium, trifluoromethyl sulfonic acid lithium, hexafluoroarsenate lithium or bis trifluoromethyl sulfimide lithium
Kind；And/or
The solvent is ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, glycol dimethyl ether, second
At least one of nitrile or methyl propyl carbonate.
The time of the solid-liquid phase reaction is 0.5h~for 24 hours in one of the embodiments,；And/or
The temperature of the solid-liquid phase reaction is 20 DEG C~30 DEG C.
It in one of the embodiments, further include by an at least side surface for lithium substrate in the preparation method of metal lithium sheet
The step of sanding and polishing processing is carried out to an at least side surface for the lithium substrate before contacting with reaction solution；And/or
It further include that metal lithium sheet is dried after forming lithium salts decorative layer on an at least side surface for lithium substrate
The step of processing.
It is described in one of the embodiments, to be dried to set the metal lithium sheet comprising lithium substrate and lithium salts decorative layer
It is dried in glove box.
A kind of energy storage device, the negative electrode material of the energy storage device are above-mentioned metal lithium sheet.
The energy storage device is lithium metal battery, lithium-air battery, lithium-sulfur cell or super in one of the embodiments,
Capacitor.
Above-mentioned metal lithium sheet includes lithium salts decorative layer, and the lithium salts decorative layer is form compact and stable to be formed in lithium substrate surface
Protective layer, the protective layer can make lithium ion uniformly through so that lithium metal uniform deposition, effectively inhibits the growth of Li dendrite.
The protective layer reduces the reactivity of lithium metal itself simultaneously, has been also prevented from lithium metal and has contacted with the direct of electrolyte, can
It effectively reduces the generation of side reaction, reduce the decomposition and consumption of electrolyte.Further, the consumption of lithium dendrite growth amount and electrolyte
The reduction of decomposition amount also inhibits repeatedly rupture of the SEI film in charge and discharge process and is formed, and can effectively promote energy storage device
Cycle life and security performance.
The preparation method of above-mentioned metal lithium sheet is simple, and lithium substrate is contacted with reaction solution, solid-liquid phase reaction is carried out, in lithium substrate
An at least side surface on form lithium salts decorative layer, reaction condition is mild, and process conditions are easy, easily operated, reproducible,
Suitable for commercially producing on a large scale.
Above-mentioned energy storage device has many advantages, such as that capacity is high, impedance is low, has extended cycle life, and meets the requirement of high-energy density,
The development for being conducive to promote the industrialization of metal lithium energy storage device, has broad application prospects.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of metal lithium sheet provided by the invention.
Fig. 2 is the structural formula of the double oxalic acid lithium phosphates of difluoro in Examples 1 to 5.
A is the SEM figure of metal lithium sheet in comparative example in Fig. 3, and b is the SEM figure of metal lithium sheet in embodiment 5.
Fig. 4 is the cycle performance figure of lithium metal battery in embodiment 1.
Fig. 5 is the cycle performance figure of symmetrical lithium metal battery and lithium metal battery symmetrical in embodiment 5 in comparative example.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give presently preferred embodiments of the present invention.But the invention can be realized in many different forms, however it is not limited to this paper institute
The embodiment of description.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more thorough
Comprehensively.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
As shown in Fig. 1, the present invention provides a kind of metal lithium sheets 10 comprising lithium substrate 11 and lithium salts decorative layer 12.
Lithium salts decorative layer 12 is set on an at least side surface for lithium substrate 11.Lithium salts decorative layer 12 with a thickness of 0.5 μm~20 μm.
In a wherein example, lithium substrate 11 is lithium piece, lithium band or lithium foil.
Preferably, lithium salts decorative layer 12 with a thickness of 0.5 μm~2.5 μm, 4 μm~8 μm, 10 μm~15 μm or 18 μm~20
μm。
It is further preferred that lithium salts decorative layer 12 with a thickness of 0.8 μm, 1 μm, 2 μm, 5 μm, 7 μm, 12 μm or 19 μm.
Lithium salts decorative layer 12 is the protective layer formed on an at least side surface for lithium substrate 11 by solid-liquid phase reaction.
In solid-liquid phase reaction, solid phase is lithium substrate 11, and liquid phase is that lithium salts is dissolved in the mixed liquor formed in solvent, and lithium substrate 11 is at least
One side surface is contacted with mixed liquor, controls time and the temperature of solid-liquid phase reaction, forms lithium salts on the corresponding surface of lithium substrate 11
Decorative layer 12.
Lithium salts decorative layer 12 is the form compact and stable protective layer formed on 11 surface of lithium substrate, which can make lithium ion
Uniformly through so that lithium metal uniform deposition, effectively inhibits the growth of Li dendrite.The protective layer reduces lithium metal itself simultaneously
Reactivity, be also prevented from directly contacting for lithium metal and electrolyte, the generation of side reaction can be effectively reduced, reduce electrolysis
The decomposition and consumption of liquid.Further, the reduction of the consumption decomposition amount of lithium dendrite growth amount and electrolyte also inhibits SEI film and is filling
Rupture repeatedly and formation in discharge process, can effectively promote the cycle life and security performance of energy storage device.
Further, the present invention also provides a kind of preparation methods of metal lithium sheet comprising following steps:
Under protective gas atmosphere, an at least side surface for lithium substrate is contacted with reaction solution, is existed by solid-liquid phase reaction
Lithium salts decorative layer is formed on the respective surfaces of the lithium substrate, obtains the metal lithium sheet comprising lithium substrate and lithium salts decorative layer；
The reaction solution is that lithium salts is dissolved in mixed liquor obtained in solvent.
Specifically, protective gas atmosphere can be but be not limited to nitrogen or inert gas (such as helium, neon and argon gas
One or more of) atmosphere.
The preparation method of metal lithium sheet is simple, by the solid-liquid phase reaction of lithium substrate and mixed liquor can lithium substrate extremely
Lithium salts decorative layer is formed on a few side surface, reaction condition is mild, and process conditions are easy, and it is easily operated, it is reproducible, it is suitable for
It commercially produces on a large scale.
In a specific example, mass percent of the lithium salts in the mixed liquor is 1%~25%.
Preferably, mass percent of the lithium salts in the mixed liquor is 1%~8%, 10%~15%, 18%~20%
Or 22%~25%.
It is further preferred that mass percent of the lithium salts in the mixed liquor be 2%, 4%, 5%, 8%, 10%,
12%, 20% or 24%.
In a specific example, the lithium salts is the double oxalic acid lithium phosphates of difluoro, LiBF4, dioxalic acid boric acid
At least one in lithium, difluorine oxalic acid boracic acid lithium, trifluoromethyl sulfonic acid lithium, hexafluoroarsenate lithium or bis trifluoromethyl sulfimide lithium
Kind；And/or
The solvent is ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, glycol dimethyl ether, second
At least one of nitrile or methyl propyl carbonate.
Preferably, the lithium salts is the double oxalic acid lithium phosphates of difluoro.
In a specific example, time of the solid-liquid phase reaction is 0.5h~for 24 hours；And/or
The temperature of the solid-liquid phase reaction is 20 DEG C~30 DEG C.
Preferably, the time of solid-liquid phase reaction is 0.5h~3h, 4h~8h, 10h~15h, 17h~19h or 20h~for 24 hours.
It is further preferred that the time of solid-liquid phase reaction be 0.8h, 1h, 1.5h, 2h, 2.5h, 5h, 6h, 11h, 12.5h,
14h, 18h, 21h or for 24 hours.
In a specific example, further include in the preparation method of metal lithium sheet with by at least side table of lithium substrate
The step of face carries out sanding and polishing processing to an at least side surface for lithium substrate before contacting with reaction solution.
In a specific example, further include in the preparation method of metal lithium sheet an at least side surface for lithium substrate it
To the withering step of metal lithium sheet after upper formation lithium salts decorative layer.
It is described to be dried to set the metal lithium sheet comprising lithium substrate and lithium salts decorative layer in a specific example
It is dried in glove box.
A kind of energy storage device, the negative electrode material of the energy storage device are above-mentioned metal lithium sheet.
In a specific example, the energy storage device is lithium metal battery, lithium-air battery, lithium-sulfur cell or super
Capacitor.
Using above-mentioned metal lithium sheet as negative electrode material, the raw materials such as corresponding positive electrode, electrolyte, diaphragm is cooperated to prepare
The energy storage devices such as lithium metal battery, lithium-air battery, lithium-sulfur cell, supercapacitor are high with capacity, impedance is low, cycle life
The advantages that long, meets the requirement of high-energy density, is conducive to the development for promoting the industrialization of metal lithium energy storage device, has wide
Application prospect.
The following are specific embodiments:
Embodiment 1
The present embodiment is prepared for a kind of metal lithium sheet, and the metal lithium sheet of preparation is assembled into lithium metal battery, and test
Its cycle performance.Specifically:
(1) preparation of metal lithium sheet
In argon atmosphere, a side surface of lithium piece is subjected to sanding and polishing processing.In argon atmosphere, by the double grass of difluoro
Acid phosphoric acid lithium is dissolved in ethylene carbonate: in the solvent of methyl ethyl carbonate=1:3 (mass ratio) composition, mixed liquor, mixing is made
The mass percent of the double oxalic acid lithium phosphates of difluoro is 2% in liquid.
In 20 DEG C of argon atmosphere, the one side after lithium piece sanding and polishing is contacted into 2h with mixed liquor, is obtained comprising lithium base
Metal lithium sheet, is then placed in glove box and is dried by the metal lithium sheet at bottom and lithium salts decorative layer.Lithium in metal lithium sheet
Salt decorative layer with a thickness of 5 μm.
(2) lithium metal battery is assembled
Metal lithium sheet after will be dry in (1) is as negative electrode material, LiFePO4 (LiFePO4) it is used as positive electrode, group
Dress up lithium metal battery, in assembling process, lithium salts decorative layer is arranged towards anode.The diaphragm of used in battery is polyethylene
Film, electrolyte are that be dissolved in mass ratio be ethylene carbonate to 1mol lithium hexafluoro phosphate: obtained in methyl ethyl carbonate=1:1 solvent
Electrolyte.
(3) cycle performance is tested
Lithium metal battery obtained in (2) is subjected to loop test, cycle performance figure such as attached drawing 4 under the current density of 1C
It is shown.By attached drawing 4 it is found that lithium metal battery still keeps higher specific capacity, and coulombic efficiency is higher after circulation 200 times.
Embodiment 2
The present embodiment is prepared for a kind of metal lithium sheet, and the metal lithium sheet of preparation is assembled into lithium metal battery, and test
Its cycle performance.Specifically:
(1) preparation of metal lithium sheet
In argon atmosphere, a side surface of lithium piece is subjected to sanding and polishing processing.In argon atmosphere, by the double grass of difluoro
Acid phosphoric acid lithium is dissolved in methyl ethyl carbonate ester solvent, and mixed liquor is made, the quality percentage of the double oxalic acid lithium phosphates of difluoro in mixed liquor
Number is 20%.
In 25 DEG C of argon atmosphere, the one side after lithium piece sanding and polishing is contacted for 24 hours with mixed liquor, is obtained comprising lithium base
Metal lithium sheet, is then placed in glove box and is dried by the metal lithium sheet at bottom and lithium salts decorative layer.Lithium in metal lithium sheet
Salt decorative layer with a thickness of 11 μm.
(2) lithium metal battery is assembled
Metal lithium sheet after will be dry in (1) is as negative electrode material, nickel-cobalt-manganese ternary material
(Li1.5Mn0.54Co0.13Ni0.13O2) it is used as positive electrode, it is assembled into lithium metal battery, in assembling process, lithium salts decorative layer direction
Anode setting.The diaphragm of used in battery is glass fibre membrane, and electrolyte is that be dissolved in mass ratio be carbon to 1mol lithium hexafluoro phosphate
Dimethyl phthalate: electrolyte obtained in methyl ethyl carbonate=1:2 solvent.
(3) cycle performance is tested
Lithium metal battery obtained in (2) is subjected to loop test under the current density of 1C, after recycling 200 times, lithium gold
Category battery specific capacity is 200mAh/g, and coulombic efficiency is higher.
Embodiment 3
The present embodiment is prepared for a kind of metal lithium sheet, and the metal lithium sheet of preparation is assembled into symmetrical lithium metal battery, and
Test its cycle performance.Specifically:
(1) preparation of metal lithium sheet
In argon atmosphere, a side surface of lithium piece is subjected to sanding and polishing processing.In argon atmosphere, by the double grass of difluoro
Acid phosphoric acid lithium is dissolved in dimethyl carbonate: in the solvent of methyl ethyl carbonate=1:2 (mass ratio) composition, mixed liquor, mixing is made
The mass percent of the double oxalic acid lithium phosphates of difluoro is 5% in liquid.
In 25 DEG C of argon atmosphere, the one side after lithium piece sanding and polishing is contacted into 5h with mixed liquor, is obtained comprising lithium base
Metal lithium sheet, is then placed in glove box and is dried by the metal lithium sheet at bottom and lithium salts decorative layer.Lithium in metal lithium sheet
Salt decorative layer with a thickness of 8 μm.
(2) lithium metal battery is assembled
Metal lithium sheet after will be dry in (1) is assembled into symmetrical lithium metal electricity as positive electrode and negative electrode material
Pond, in assembling process, lithium salts decorative layer is oppositely arranged.The diaphragm of used in battery is glass fibre membrane, and electrolyte is 1mol hexafluoro
It is dimethyl carbonate: electrolyte obtained in methyl ethyl carbonate=1:3 solvent that lithium phosphate, which is dissolved in mass ratio,.
(3) cycle performance is tested
By symmetrical lithium metal battery obtained in (2) in 1.0mA/cm2Current density, 1.0mA/cm2Deposit capacity under into
Row test.After 400h is recycled, symmetrical lithium metal battery performance is stable and polarization is lower.
Embodiment 4
The present embodiment is prepared for a kind of metal lithium sheet, and the metal lithium sheet of preparation is assembled into symmetrical lithium metal battery, and
Test its cycle performance.Specifically:
(1) preparation of metal lithium sheet
In argon atmosphere, a side surface of lithium piece is subjected to sanding and polishing processing.In argon atmosphere, by the double grass of difluoro
Acid phosphoric acid lithium is dissolved in glycol dinitrate ether solvents, and mixed liquor is made, the quality hundred of the double oxalic acid lithium phosphates of difluoro in mixed liquor
Score is 10%.
In 25 DEG C of argon atmosphere, the one side after lithium piece sanding and polishing is contacted into 5h with mixed liquor, is obtained comprising lithium base
Metal lithium sheet, is then placed in glove box and is dried by the metal lithium sheet at bottom and lithium salts decorative layer.Lithium in metal lithium sheet
Salt decorative layer with a thickness of 12 μm.
(2) lithium metal battery is assembled
Metal lithium sheet after will be dry in (1) is assembled into symmetrical lithium metal electricity as positive electrode and negative electrode material
Pond, in assembling process, lithium salts decorative layer is oppositely arranged.The diaphragm of used in battery is polypropylene, polyethylene film, electrolyte 1mol
Lithium hexafluoro phosphate is dissolved in electrolyte obtained in glycol dinitrate ether solvents.
(3) cycle performance is tested
By symmetrical lithium metal battery obtained in (2) in 1.0mA/cm2Current density, 1.0mA/cm2Deposit capacity under into
Row test.After 600h is recycled, symmetrical lithium metal battery performance is stable and polarization is lower.
Embodiment 5
The present embodiment is prepared for a kind of metal lithium sheet, and the metal lithium sheet of preparation is assembled into symmetrical lithium metal battery, and
Test its cycle performance.Specifically:
(1) preparation of metal lithium sheet
In argon atmosphere, a side surface of lithium piece is subjected to sanding and polishing processing.In argon atmosphere, by the double grass of difluoro
Acid phosphoric acid lithium is dissolved in methyl ethyl carbonate ester solvent, and mixed liquor is made, the quality percentage of the double oxalic acid lithium phosphates of difluoro in mixed liquor
Number is 15%.
In 25 DEG C of argon atmosphere, the one side after lithium piece sanding and polishing is contacted for 24 hours with mixed liquor, is obtained comprising lithium base
Metal lithium sheet, is then placed in glove box and is dried by the metal lithium sheet at bottom and lithium salts decorative layer.Lithium in metal lithium sheet
Salt decorative layer with a thickness of 15 μm.The SEM of metal lithium sheet after drying schemes as shown in b in attached drawing 3.
(2) lithium metal battery is assembled
Metal lithium sheet after will be dry in (1) is assembled into symmetrical lithium metal electricity as positive electrode and negative electrode material
Pond, in assembling process, lithium salts decorative layer is oppositely arranged.The diaphragm of used in battery is polyethylene film, and electrolyte is 1mol hexafluoro phosphorus
Sour lithium is dissolved in ethylene carbonate: electrolyte obtained in methyl ethyl carbonate=1:2 (mass ratio) solvent.
(3) cycle performance is tested
By symmetrical lithium metal battery obtained in (2) in 1.0mA/cm2Current density, 1.0mA/cm2Deposit capacity under into
Row test, test result are as shown in Fig. 5.By attached drawing 5 it is found that after 800h is recycled, symmetrical lithium metal battery performance is stablized
And polarization is lower.
Embodiment 6
The present embodiment is prepared for a kind of metal lithium sheet, and the metal lithium sheet of preparation is assembled into symmetrical lithium metal battery, and
Test its cycle performance.Specifically:
(1) preparation of metal lithium sheet
In argon atmosphere, a side surface of lithium piece is subjected to sanding and polishing processing.In argon atmosphere, by tetrafluoro boric acid
Lithium is dissolved in methyl ethyl carbonate ester solvent, and mixed liquor is made, and the mass percent of LiBF4 is 2% in mixed liquor.
In 20 DEG C of argon atmosphere, the one side after lithium piece sanding and polishing is contacted into 2h with mixed liquor, is obtained comprising lithium base
Metal lithium sheet, is then placed in glove box and is dried by the metal lithium sheet at bottom and lithium salts decorative layer.Lithium in metal lithium sheet
Salt decorative layer with a thickness of 10 μm.
(2) lithium metal battery is assembled
Metal lithium sheet after will be dry in (1) is assembled into symmetrical lithium metal electricity as positive electrode and negative electrode material
Pond, in assembling process, lithium salts decorative layer is oppositely arranged.The diaphragm of used in battery is polyethylene film, and electrolyte is 1mol hexafluoro phosphorus
Sour lithium is dissolved in ethylene carbonate: electrolyte obtained in methyl ethyl carbonate=1:1 (mass ratio) solvent.
(3) cycle performance is tested
By symmetrical lithium metal battery obtained in (2) in 1.0mA/cm2Current density, 1.0mA/cm2Deposit capacity under into
Row test, after 400h is recycled, symmetrical lithium metal battery performance is stable and polarization is lower.
Comparative example
In this comparative example under argon atmosphere, by lithium piece side surface polishing, does not form lithium salts on a surface and repair
Layer is adornd, it is then dry in glove box.The SEM on the surface after lithium piece sanding and polishing after drying schemes as shown in a in attached drawing 3.It will
Lithium piece in this comparative example after the surface polishing of side is assembled into symmetrical lithium metal battery respectively, and carries out cycle performance survey
Examination.Specifically:
(1) symmetrical lithium metal battery is assembled
Lithium piece after will be dry in this comparative example is assembled into symmetrical lithium metal electricity as positive electrode and negative electrode material
Pond, in assembling process, lithium piece sanding and polishing is oppositely arranged on one side.The diaphragm of used in battery is polyethylene film, and electrolyte is
1mol lithium hexafluoro phosphate is dissolved in ethylene carbonate: electrolyte obtained in methyl ethyl carbonate=1:2 (mass ratio) solvent.
(2) cycle performance is tested
By symmetrical lithium metal battery obtained in (2) in 1.0mA/cm2Current density, 1.0mA/cm2Deposit capacity under into
Row test, test result are as shown in Fig. 5.By attached drawing 5 it is found that symmetrical lithium metal battery circulation time is less than 300h, and polarize
It is very big.
By b in a in attached drawing 3 and attached drawing 3 it is found that after solid-liquid phase reaction, lithium piece surface forms fine and close protection circle
Face.
By attached drawing 5 it is found that compared with the metal lithium sheet for not forming lithium salts decorative layer, the metal lithium sheet containing lithium salts decorative layer
The symmetrical lithium metal battery polarization phenomena being assembled into obviously weaken.Do not formed lithium salts decorative layer metal lithium sheet be assembled into it is symmetrical
Lithium metal battery circulation time occurs as soon as serious polarization phenomena less than 300h, higher overpotential occurs；It is modified containing lithium salts
The symmetrical lithium metal battery that the metal lithium sheet of layer is assembled into still maintains lower overpotential after 800h is recycled.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of metal lithium sheet, it is characterised in that: including lithium substrate and lithium salts decorative layer, the lithium salts decorative layer is set to the lithium
On an at least side surface for substrate；The lithium salts decorative layer with a thickness of 0.5 μm~20 μm.
2. metal lithium sheet as described in claim 1, it is characterised in that: the lithium substrate is lithium piece, lithium band or lithium foil.
3. a kind of preparation method of metal lithium sheet, characterized by the following steps:
Under protective gas atmosphere, an at least side surface for lithium substrate is contacted with reaction solution, by solid-liquid phase reaction described
Lithium salts decorative layer is formed on the respective surfaces of lithium substrate, obtains the metal lithium sheet comprising lithium substrate and lithium salts decorative layer；It is described
Reaction solution is that lithium salts is dissolved in mixed liquor obtained in solvent.
4. the preparation method of metal lithium sheet as claimed in claim 3, it is characterised in that: the matter of the lithium salts in the reaction solution
Measuring percentage is 1%~25%.
5. the preparation method of metal lithium sheet as claimed in claim 4, it is characterised in that: the lithium salts is the double oxalic acid phosphoric acid of difluoro
Lithium, LiBF4, dioxalic acid lithium borate, difluorine oxalic acid boracic acid lithium, trifluoromethyl sulfonic acid lithium, hexafluoroarsenate lithium or double fluoroforms
At least one of base sulfimide lithium；And/or
The solvent be ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, glycol dimethyl ether, acetonitrile or
At least one of methyl propyl carbonate.
6. the preparation method of metal lithium sheet as claimed in claim 3, it is characterised in that: the time of the solid-liquid phase reaction is 0.5h
~for 24 hours；And/or
The temperature of the solid-liquid phase reaction is 20 DEG C~30 DEG C.
7. the preparation method of metal lithium sheet as described in any one of claim 3~6, it is characterised in that: further include by lithium substrate
An at least side surface contacted with reaction solution before the step of sanding and polishing processing is carried out at least side surface of the lithium substrate
Suddenly；And/or
It further include that metal lithium sheet is dried after forming lithium salts decorative layer on an at least side surface for lithium substrate
The step of.
8. the preparation method of metal lithium sheet as claimed in claim 7, it is characterised in that: described to be dried as that include lithium substrate
It is placed in glove box and is dried with the metal lithium sheet of lithium salts decorative layer.
9. a kind of energy storage device, it is characterised in that: the negative electrode material of the energy storage device is any one of such as claim 1~2 institute
State metal lithium sheet.
10. energy storage device as claimed in claim 9, it is characterised in that: the energy storage device is lithium metal battery, lithium air electricity
Pond, lithium-sulfur cell or supercapacitor.
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| CN112864349A (en) * | 2021-03-09 | 2021-05-28 | 南京航空航天大学 | Negative electrode with protective layer, preparation method of negative electrode and secondary battery |
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