CN109841836A - A kind of compound metal lithium electrode of gel and its preparation method and application - Google Patents
A kind of compound metal lithium electrode of gel and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to compound metal lithium electrodes of a kind of gel and its preparation method and application, belong to technical field of lithium ion.The electrode is made of collector, lithium metal layer and gel layer thereon, and the lithium metal layer fitting on a current collector, is pressed on collector by roll-in by lithium piece and is obtained；Gel layer is generated by the method for uv photopolymerization in lithium metal piece surface in situ by the polymerization precursor liquid being coated on lithium metal layer, and polymerization precursor liquid is made of polymer P VDF-HFP, photopolymerizer ETPTA, photoinitiator HMPP, lithium salts, metal oxide nano additive and ether solvent.The invention also discloses the compound metal lithium electrode of gel and it lithium metal battery preparation in application.The method of the present invention is simple and easy, and the compound metal lithium electrode of gel obtained can be used directly, can also stablize circulation under high current density high capacity, and no Li dendrite generates；Meanwhile electrode sheet electron insulate, when assembled battery, can remove diaphragm, can effectively improve the energy density of battery.
Description
Technical field
The present invention relates to compound metal lithium electrodes of a kind of gel and its preparation method and application, are coated by polymer gel
Means prepare metal lithium electrode, then prepare lithium metal battery with the electrode, belong to technical field of lithium ion.
Background technique
By the development of recent two decades, lithium ion battery has come into thousand by its efficient, convenient, free of contamination characteristic
Ten thousand families of family, however, with the portable mobile equipment using mobile phone as representative and the new energy vehicles by representative of electric car
Fast development, people propose increasingly higher demands to lithium ion battery, in particular with " stand-by time is worried " and " inner
The intensification of journey worry ", allows people especially to value the energy density of lithium ion battery.In this context, traditional negative electrode material stone
Ink, capacity potentiality are dug to the greatest extent by basic, and the novel anode materials such as silicium cathode, lithium titanate be also difficult to meet consumer it is intimate
Unlimited capacity requirement.Therefore, sight has been turned to lithium an- ode by more and more researchers.Relative to other cathode materials
Material, lithium metal possess minimum reversible potential (- 3.04V vs SHE), highest theoretical capacity (3860mAh/g), therefore, lithium
Metal is considered as the ideal negative electrode material of next-generation lithium ion battery, new especially for lithium-air battery, lithium-sulfur cell etc.
System battery only can just give full play to its high-energy-density advantage using lithium metal.Just once there is the seventies and eighties in last century lithium golden
Belong to battery to emerge, however, being had been found that in use process, directly uses cathode of the lithium metal as battery, during the charging process can
A large amount of Li dendrite is generated, Li dendrite readily penetrates through diaphragm, and battery short circuit is caused even to cause fire.To find out its cause, lithium is golden
Category no doubt possess it is all how far the advantage of super other materials, while also having and being much difficult to taming " wild nature ".
The reactivity of lithium metal is extremely strong, can almost react with all liquid electrolytes touched, in battery
Charging process in, lithium metal reacts with electrolyte, generates one layer of solid electrolyte film (SEI film), SEI film can prevent
The lithium metal generated in deposition process is by electrolytic corrosion.But as the lithium metal of deposition is more and more, lithium metal is deposited not
, non-uniform deposition morphology can be generated, Li dendrite is formed, bursts SEI film, or even penetrate diaphragm and cause battery short circuit.In addition,
Newborn lithium is constantly consumed, and is caused " the dead lithium " that can not recycle and is constantly consumed electrolyte, cathode dusting is caused to fail.For solution
The certainly above problem, to enable lithium metal to be really applied in battery, scientific research personnel protects cathode of lithium using various methods,
Inhibit Li dendrite.
There is researcher using the material building frame that density is smaller, chemical/electrochemical is stable, lithium is deposited in frame
Portion, reduces local current densities with this, provides deposition space for lithium metal, inhibits Li dendrite with this.(Nature
Nanotechnology 2016,11:626–632；Nature Communications 2016,7:10992；Journal of
Physical Chemistry Letters,2016,7(7):1267；Advanced Materials 2017,1700389.) so
And material specific surface area is although improved using such method, local current densities are reduced, but cannot be guaranteed the equal of lithium metal
Even deposition, just not can guarantee yet and does not generate Li dendrite.In addition, such method is there is also material hole utilization rate is low, charge and discharge electricity
Therefore the small problem of current density can not give full play to the advantage of lithium an- ode.Another thinking is on cathode of lithium surface
One layer of manual construction firm SEI film such as coats LiPO on lithium surface using interface engineering gimmick3、Al2O3Or the substances such as BN.
(Advanced Materials,2016,28:1853–1858；Acs Nano,2015,9(6):5884；Nano
Letter.2014,14:6016-6022.) such method can be effectively improved the deposition properties of lithium, but difficulty of processing is very big, and it is difficult
It is used with universal.Also studies have found that, copolymer solid electrolyte such as β-PVDF, PVDF-HFP, Al are used2O3/ PVDF-HFP etc.
Film cladding cathode of lithium can also be effectively improved the deposition properties of lithium.(Advanced Energy Materials,2017,
1701482；Advanced Functional Materials.2018,1705838；Advanced Materials,2016,
28,857-863.) however, directly using copolymer solid electrolyte cladding cathode of lithium, that there is also ionic conductivities is lower, lithium is negative
The larger problem of contact resistance between pole and polymer film, and the diaphragm use that generally also to arrange in pairs or groups again in article, cannot be intuitive
Assert that polymer solid electrolyte film can prevent completely Li dendrite.In addition, in new systems batteries such as lithium-air batteries in recent years
In research, there is scholar to use the mode of photopolymerization gel, PVDF-HFP be dissolved into NMP, then is shone with light curing agent mixed light,
Cathode of lithium is thereby protected, battery performance also has some improvement.(Advanced Materials,2016,DOI:10.1002/
adma.201602800；Angewandte Chemie International Edition, 2017,56,7505-7509.) but
It is that in such method, NMP will be always present in gel, and thermodynamically, and NMP is reacted with lithium, causes to occur uncontrollable
Side reaction, and cause the destruction of gel layer and cathode of lithium.
Summary of the invention
The present invention devises a kind of compound metal lithium electrode of gel and preparation method thereof, and stabilization is prepared with the electrode
Circulation, safe and reliable lithium metal battery.
The present invention proposes a kind of new method, i.e., by polymer P VDF-HFP, light curing agent ETPTA, photoinitiator HMPP,
Lithium salts and additive are dissolved directly into ether solvent, are uniformly coated on the surface of lithium, and the cured method of ultraviolet light is reused
Photopolymerization gel layer in situ coats cathode of lithium.Such method is simple and easy, and gained gel layer is steady to metal lithium electrode chemical property
It is fixed, and gel has certain flexibility, can greatly improve lithium deposition section, optimizes lithium deposition process.With gel made from this
Compound metal lithium electrode can be used directly, can also stablize circulation under high current density high capacity, and no Li dendrite generates；Together
When, electrode sheet electron insulation, when assembled battery, can remove diaphragm, can effectively improve the energy density of battery.
A kind of compound metal lithium electrode of gel is made of collector, lithium metal layer and gel layer thereon, the lithium gold
Belong to layer fitting on a current collector, is pressed on collector and is obtained by roll-in by lithium piece；The gel layer is by being coated in lithium metal
Photopolymerization precursor liquid on layer is generated by the method for uv photopolymerization in lithium metal surface in situ, the photopolymerization precursor liquid
By polymer P VDF-HFP (Kynoar-hexafluoropropylene copolymer), photopolymerizer ETPTA (ethoxylation trihydroxy methyl third
Alkane triacrylate), photoinitiator HMPP (2- hydroxy-2-methyl -1- phenyl -1- acetone), lithium salts, metal oxide nano add
Agent and ether solvent is added to form.
Preferably, in the photopolymerization precursor liquid, lithium salts is LiTFSI (double trifluoromethanesulfonimide lithiums), LiNO3、
LiFSI (double fluorine sulfimide lithiums), LiCF3SO3、LiClO4And LiPF6One or more of；Metal oxide nano addition
Agent is nanoscale Al2O3、SiO2, one or more of LAGP (phosphoric acid germanium aluminium lithium) and LATP (titanium phosphate aluminium lithium)；Ether solvent
For one or more of dimethyl ether, glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethyleneglycol dimethyl ether, in ether solvent
1,3- dioxolanes and/or 4- methyl-1,3- dioxolanes can also additionally be added.
Preferably, in the photopolymerization precursor liquid, the mass ratio of ETPTA and PVDF-HFP in 2:1 between 5:1,
HMPP is between the 0.05% to 5% of ETPTA mass；The mass ratio of three's gross mass and ether solvent 1:4 to 1:1 it
Between.In photopolymerization precursor liquid, the concentration of the lithium salts is in 0.1mol/L between 5mol/L；The nanometer additive
Mass fraction is between 1% to 25%.
Preferably, the coating thickness of the photopolymerization precursor liquid is between 5 μm to 500 μm.
A kind of preparation method of the compound metal lithium electrode of gel, includes the following steps:
(1) photopolymerization precursor liquid is prepared: by polymer P VDF-HFP, photopolymerizer ETPTA, photoinitiator HMPP, lithium salts
It is dissolved into ether solvent, is uniformly mixed with oxidate nano additive；
(2) it coats: first on a current collector by lithium metal piece roll-in fitting, then coating polymerization forerunner in lithium metal layer surface
Liquid layer；
(3) ultraviolet light solidifies: photopolymerization forerunner's liquid layer being carried out ultraviolet light solidification, obtains the compound metal lithium electrode of gel.
Preferably, the collector is copper foil, copper mesh, aluminium foil, aluminium net, stainless steel foil or stainless (steel) wire；Lithium metal piece
It is bonded between collector by roll-in.Can soldering polar ear on a current collector, or directly draw from collector or lithium piece
Line is as tab.
Preferably, in the material for preparing photopolymerization precursor liquid, lithium salts LiTFSI, LiNO3、LiFSI、LiCF3SO3、
LiClO4、LiPF6One or more of；Additive is nanoscale Al2O3、SiO2, one or more of LAGP or LATP；Ether
Class solvent is dimethyl ether, glycol dimethyl ether, triethylene glycol dimethyl ether and/or tetraethyleneglycol dimethyl ether, can volume in ether solvent
Outer addition 1,3- dioxolanes and/or 4- methyl-1,3- dioxolanes.
Preferably, in the preparation method of the compound metal lithium electrode of gel, the mass ratio of ETPTA and PVDF-HFP 2:1 extremely
Between 5:1, HMPP is between the 0.05% to 5% of ETPTA mass.Three's gross mass and the ratio of organic solvent are in 1:4 to 1:1
Between.The concentration of the lithium salts in organic solvent is in 0.1mol/L between 5mol/L.The nanometer additive is solidifying
Mass fraction in glue precursor liquid is between 1% to 25%.
Preferably, photopolymerization precursor liquid is coated in lithium metal surface, coating method is knife coating or spin-coating method.More preferably,
Precursor liquid coating thickness is between 5 μm to 500 μm.
Preferably, ultraviolet wavelength range should be less than 395nm, and the time of photocuring is 10-60s.
Preferably, aforesaid operations (coating and ultraviolet light solidification) carry out in drying room or glove box.
The compound metal lithium electrode of gel of the invention is applied in lithium metal battery preparation, and lithium metal battery can be effectively improved
Cyclical stability.
Beneficial effects of the present invention: the method for the present invention is simple and easy, and the compound metal lithium electrode of gel obtained can be direct
It uses, circulation can also be stablized under high current density high capacity, no Li dendrite generates；Meanwhile electrode sheet electron insulate, assembling
Diaphragm can be removed when battery, can effectively improve the energy density of battery.
Detailed description of the invention
Fig. 1 is the compound metal lithium electrode preparation method schematic diagram of gel；
Fig. 2 is unshielded metal lithium electrode work rear surface/section electron microscope；
Fig. 3 is the compound metal lithium electrode work rear surface/section electron microscope of gel；
Fig. 4 is the cycle performance of " experimental cell " in comparative experiments 1；
Fig. 5 is the cycle performance of " control cell " in comparative experiments 1；
Fig. 6 is in comparative experiments 2 using the logarithm of gel layer ionic conductivity after the doping of different proportion nanometer additive；
Fig. 7 is to assemble Li-O using gel complex lithium metal electrode in embodiment 32The cyclic curve figure of battery.
Main appended drawing reference explanation:
1 lithium metal, 2 collector
The photopolymerization gel layer in situ of 3 negative electrode lug 4
Specific embodiment
The compound metal lithium electrode of gel of the invention is made of lithium metal layer and gel layer.Gel layer is by the inclined fluorine of polymer poly
Ethylene-hexafluoropropylene copolymer (PVDF-HFP) and photopolymerizer ethoxylated trimethylolpropane triacrylate (ETPTA)
And photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- acetone (HMPP), lithium salts, nanometer additive and ethers electrolyte are via purple
The method of outer photopolymerization is generated in lithium metal surface in situ.
As shown in Figure 1, then cutting out firstly, lithium metal piece 1 is fitted on collector 2 by roll-in；Collector 2 is
Copper foil/copper mesh, aluminium foil/aluminium net or stainless steel foil/stainless (steel) wire.Then negative electrode lug 3 is welded on collector 2, later in lithium metal
1 surface of piece coats photopolymerization precursor liquid, photocuring is carried out, in lithium metal surface in situ photopolymerization gel layer 4.It is solidifying to prepare photopolymerization
It is first that polymer P VDF-HFP, light curing agent ETPTA, photoinitiator HMPP, lithium salts and additive is direct in the method for glue
It is dissolved into ether solvent, is uniformly mixed and photopolymerization precursor liquid is made, lithium metal surface cure is arrived in re-coating.
Respectively to surface/section after unshielded metal lithium electrode and the compound metal lithium electrode work of gel of the invention
It is observed, as shown in Fig. 2, generating a large amount of Li dendrites after the work of unshielded metal lithium electrode, lithium deposition is uneven, sedimentary
There are a large amount of cavities.As shown in figure 3, the compound metal lithium electrode work rear surface of gel is stretched out without dendrite, observation section discovery, lithium sinks
Product is uniformly closely knit.
Embodiment 1
A kind of preparation method of the compound metal lithium electrode of gel, method are as follows:
(1) PVDF-HFP is mixed with ETPTA (containing 0.5wt%HMPP) by the mass ratio of 1:2, mixed with polymers is added
3 times of amount of substance of 1M LiClO4TEGDME (triethylene glycol dimethyl ether) solution, and the Nano-meter SiO_2 of gross mass 5% is added2Powder is mixed
Conjunction stirs evenly, and photopolymerization precursor liquid is made.
(2) by lithium piece (80 μm) roll-in to copper foil (9 μm), roll-in is cut out lithium piece and copper foil together to 5* to 70 μm
5cm welds negative electrode lug on copper foil, scratches gel precursor liquid, 120 μm of blade coating height on lithium piece surface.
(3) ultraviolet lamp wavelength of light 365nm is set, irradiates gel precursor liquid photocuring 30s, single side gel is made with this
Compound metal lithium electrode.
Embodiment 2
A kind of preparation method of the compound metal lithium electrode of gel, method are as follows:
(1) PVDF-HFP and ETPTA (containing 1%HMPP) are mixed in the ratio of 1:3, mixed with polymers amount of substance is added
1.5 times of 0.6M LiTFSI&0.4M LiNO3DOL/DME solution, and the nanometer Al of gross mass 10% is added2O3Powder mixes
Conjunction stirs evenly, and photopolymerization precursor liquid is made.
(2) one layer of copper mesh (10 μm) is pressed from both sides between two panels lithium piece (100 μm), two-sided lithium piece electrode is made in roll-in.Use spin coating
Method, in the photopolymerization precursor liquid of 30 μ m thick of lithium piece upper surface spin coating.
(3) ultraviolet lamp wavelength of light 365nm is set, gel precursor liquid photocuring 20s is irradiated.Overturning electrode, another
Face equally coats 30 μ m thick gel precursor liquids, same photocuring 20s.
(4) negative electrode lug is drawn on copper mesh, and two-sided gel complex lithium metal electrode is made.
Comparative experiments 1
By document Advanced Materials, method described in 2016, DOI:10.1002/adma.201602800, first
PVDF-HFP is dissolved into NMP, 20% solution is made into, is denoted as solution 1；Again in the ratio of PVDF-HFP:ETPTA=1:3
ETPTA is added in solution 1 and the HMPP of ETPTA mass 0.1% is added, mixing is denoted as solution 2；It adds and the equal bodies of solution 2
Long-pending 1M LiCF3SO3TEGDME solution, mixing be denoted as solution 3；Solution 3 is coated onto lithium piece surface, illumination polyase 13 0s is obtained
Compound metal lithium electrode is denoted as " reference electrode ", takes the identical reference electrode assembling Symmetrical cells of two panels, is denoted as " control electricity
Pond ".
Compound metal lithium electrode obtained in another Example 1, is denoted as " experimental electrode ", takes the identical experimental electrode of two panels
Symmetrical cells are assembled in the same way, are denoted as " experimental cell ".
It is 0.5mA/cm that " control cell " and " experimental cell " is arranged to current density simultaneously2, constant volume 6mAh/cm2Constant volume
Circulation, comparison loop performance.As shown in Figure 4 and Figure 5, " experimental cell " stablizes circulation 1400h or more, and charge and discharge overpotential is stablized
Within 20mV, and " control cell " cyclic curve is extremely unstable, and charging overpotential can reach 450mV or more, can by comparison
When absolutely proving containing non-ether solvents such as NMP, gel layer is to lithium and unstable.
Comparative experiments 2
By experimental method as described in example 2, PVDF-HFP and ETPTA (containing 1%HMPP) are mixed in the ratio of 1:3,
1.5 times of mixed with polymers amount of substance of 0.6M LiTFSI&0.4M LiNO is added3DOL/DME solution, then be separately added into difference
The Nano-sized Alumina Powder of ratio, make nano aluminium oxide difference the total mixed liquor quality of Zhan 0% (being not spiked with), 5%, 10%,
20%, photopolymerization forms gel layer, tests the ionic conductivity of different gel layers at room temperature.As shown in fig. 6, discovery is mixed
Add (5%, 10%, 20% group) after nano aluminium oxide, the ionic conductivity of gel layer is relatively not spiked with nano aluminium oxide (0%
Group), ionic conductivity has more than the promotion of an order of magnitude.
Embodiment 3
Cathode is done using the compound metal lithium electrode of gel prepared in embodiment 1, uses 1M LiClO4TEGDME solution
Electrolyte is done, carbon carrying capacity 1mg/cm is used2Super-P electrode as air electrode, assemble Li-O20.1mA/ is arranged in battery
cm2, constant volume 2mAh/cm2(i.e. 2000mAh/g) circulation.As shown in fig. 7, battery stablizes circulation 20 weeks.
The above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although above-described embodiment to the present invention into
Gone detailed description, the related technical personnel of this field it is understood that can modify to the present invention or replace on an equal basis, but
Any modification and part replacement for not departing from spirit and scope of the invention should all be covered in scope of the presently claimed invention.
Claims (10)
1. a kind of compound metal lithium electrode of gel, it is characterised in that: a kind of compound metal lithium electrode of gel, by collector, lithium gold
Belong to layer and gel layer composition thereon, the lithium metal layer is bonded on a current collector, is pressed onto collector by roll-in by lithium piece
On obtain；The gel layer is golden in lithium by the method for uv photopolymerization by the photopolymerization precursor liquid for being coated in lithium metal on piece
Belong to piece surface in situ to generate, the photopolymerization precursor liquid is by polymer P VDF-HFP, photopolymerizer ETPTA, photoinitiator
HMPP, lithium salts, metal oxide nano additive and ether solvent composition.
2. the compound metal lithium electrode of gel according to claim 1, it is characterised in that: in the photopolymerization precursor liquid,
Lithium salts is LiTFSI, LiNO3、LiFSI、LiCF3SO3、LiClO4And LiPF6One or more of；Metal oxide nano adds
Adding agent is nanoscale Al2O3、SiO2, one or more of LAGP and LATP；Ether solvent be dimethyl ether, glycol dimethyl ether,
One or more of triethylene glycol dimethyl ether and tetraethyleneglycol dimethyl ether；1,3- dioxy ring is additionally added in the ether solvent
Pentane and/or 4- methyl-1,3- dioxolanes.
3. the compound metal lithium electrode of gel according to claim 2, it is characterised in that: in the polymerization precursor liquid,
For the mass ratio of ETPTA and PVDF-HFP in 2:1 between 5:1, HMPP is between the 0.05% to 5% of ETPTA mass；Three is total
The mass ratio of quality and ether solvent is in 1:4 between 1:1；The concentration of the lithium salts 0.1mol/L to 5mol/L it
Between；The mass fraction of the metal oxide nano additive is between 1% to 25%.
4. the preparation method of the compound metal lithium electrode of gel according to any one of claim 1-3, includes the following steps:
(1) preparation polymerization precursor liquid: by polymer P VDF-HFP, photopolymerizer ETPTA, photoinitiator HMPP, lithium salts and nanometer
Additive is dissolved into ether solvent, is uniformly mixed；
(2) it coats: first on a current collector by the fitting of lithium metal piece, then coating polymerization forerunner's liquid layer on lithium metal piece surface；
(3) ultraviolet light solidifies: photopolymerization forerunner's liquid layer being carried out ultraviolet light solidification, obtains the compound metal lithium electrode of gel.
5. the preparation method of the compound metal lithium electrode of gel according to claim 4, it is characterised in that: the collector
For copper foil, copper mesh, aluminium foil, aluminium net, stainless steel foil or stainless (steel) wire；Between the lithium metal piece and collector by roll-in into
Row fitting.
6. the preparation method of the compound metal lithium electrode of gel according to claim 5, it is characterised in that: weld on a current collector
Tab is connect, or directly from lead on collector or lithium piece as tab.
7. the preparation method of the compound metal lithium electrode of gel according to claim 4, it is characterised in that: the coating side
Method is knife coating or spin-coating method；Photopolymerization precursor liquid coating thickness is between 5 μm to 500 μm.
8. the preparation method of the compound metal lithium electrode of gel according to claim 4, it is characterised in that: solidify in ultraviolet light
In, ultraviolet wavelength is less than 395nm, and the time of photocuring is 10-60s.
9. the preparation method of the compound metal lithium electrode of gel according to claim 4, it is characterised in that: the coating and
Ultraviolet light solidification process should carry out in drying room or glove box.
10. the compound metal lithium electrode of gel according to any one of claim 1-3 answering in lithium metal battery preparation
With.
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| CN112542562B (en) * | 2019-09-23 | 2022-10-28 | 郑州宇通集团有限公司 | Method for preparing protective layer on surface of lithium-containing metal strip, lithium-copper composite strip cathode and preparation method thereof, and lithium battery |
| CN110797506A (en) * | 2019-10-10 | 2020-02-14 | 武汉瑞科美新能源有限责任公司 | Composite lithium metal negative electrode material, preparation method and application thereof, and lithium metal battery |
| CN114530589A (en) * | 2020-11-23 | 2022-05-24 | 宁德时代新能源科技股份有限公司 | Lithium metal negative electrode, preparation method thereof, and lithium metal battery and device related to lithium metal negative electrode |
| WO2022105614A1 (en) * | 2020-11-23 | 2022-05-27 | 宁德时代新能源科技股份有限公司 | Lithium metal negative electrode, preparation method therefor and related lithium metal battery thereof, and device |
| CN114530589B (en) * | 2020-11-23 | 2023-10-17 | 宁德时代新能源科技股份有限公司 | Lithium metal negative electrode, preparation method thereof, and related lithium metal battery and device |
| CN112467258A (en) * | 2020-11-25 | 2021-03-09 | 北京航空航天大学 | Preparation method of lithium-air battery based on gel electrolyte-lithium cathode integrated structure |
| CN114725502A (en) * | 2022-04-24 | 2022-07-08 | 长沙理工大学 | Solid electrolyte membrane and preparation method and application thereof |
| CN114744158A (en) * | 2022-05-18 | 2022-07-12 | 中南大学 | Method for applying organic/inorganic composite coating to surface modification of lithium metal electrode |
| CN114744158B (en) * | 2022-05-18 | 2024-05-03 | 中南大学 | Method for modifying surface of lithium metal electrode by using organic/inorganic composite coating |
| CN115347150A (en) * | 2022-08-29 | 2022-11-15 | 中电科能源有限公司 | Surface modification method for metal lithium cathode |
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