CN109786675A - Interface modification method for metal lithium cathode of solid-state lithium battery - Google Patents
Interface modification method for metal lithium cathode of solid-state lithium battery Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 120
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910052751 metal Inorganic materials 0.000 title abstract description 10
- 239000002184 metal Substances 0.000 title abstract description 10
- 238000002715 modification method Methods 0.000 title abstract 2
- 239000007787 solid Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 39
- 239000011888 foil Substances 0.000 claims description 30
- 239000005518 polymer electrolyte Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- 230000000996 additive effect Effects 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 4
- 239000006193 liquid solution Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- 229910000521 B alloy Inorganic materials 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 229960002645 boric acid Drugs 0.000 claims description 3
- 235000010338 boric acid Nutrition 0.000 claims description 3
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 26
- 230000008569 process Effects 0.000 description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 2
- 229910012653 LiNi0.5Co0.2Mn0.3 Inorganic materials 0.000 description 2
- 229910006270 Li—Li Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910010942 LiFP6 Inorganic materials 0.000 description 1
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Substances CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- -1 hexafluoroarsenate lithium Chemical compound 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an interface modification method of a lithium metal cathode of a solid lithium battery, which adopts a mode of generating a gel polymer in situ to form a modification layer on the surface of the lithium metal. The precursor of the gel polymer contains 1,3 dioxolane solvent (DOL) which can generate in-situ ring-opening polymerization under the action of specific lithium salt, and also contains a plurality of additives which can form a stable SEI film on the surface of lithium metal. The precursor can be subjected to in-situ polymerization on the surface of the metal lithium electrode in a simple heating mode to form a DOL oligomer modified buffer layer with viscoelasticity. The invention can improve the interface physical contact between the metal lithium electrode and the solid electrolyte, thereby reducing the interface impedance. Meanwhile, a stable SEI film can be formed on the surface of the metal lithium, and the cycle performance of the solid lithium battery is favorably improved.
Description
Technical field
The invention belongs to solid state lithium battery technical fields, more particularly to a kind of directly in the life of lithium anode surface in situ
At the method for gelatin polymer interface-modifying layer.
Background technique
At present in lithium ion battery, due to largely using the inflammable organic electrolytes such as esters, ethers, there are serious
Security risk, when battery is because of any reason short circuit, battery self-energy can release in the form of heat in the short time, light
These ethers as solvent cause explosion.With the solid state battery of nonflammable solid electrolyte substitution organic electrolyte, have
Hope the safety for significantly promoting battery.
For the solid state battery for obtaining high-energy-density, battery cathode is needed using lithium metal.But in solid state lithium battery development
In the process, there are many problems demands to solve the problem of wherein very prominent in relation to lithium anode, specific manifestation are as follows: one, gold
Belong to the good microscopic contact for being difficult to obtain between lithium electrode and solid electrolyte in similar liquids electrolyte system, especially passes through
Multiple charge and discharge, since " dissolution and the deposition " of lithium metal itself will cause biggish volume change, this is further degrading lithium
Interfacial contact between solid electrolyte, so that high rate performance and cycle performance all sharp-decays of solid state lithium battery.Two, golden
Belong to lithium electrode in charge and discharge process, since surface reaction is uneven, it is easy to generate dendrite, dendrite is caused to puncture short circuit.Three,
It is likely to occur chemistry or electrochemistry side reaction between metal lithium electrode and certain solid electrolyte materials, not only causes the loss of lithium
And a large amount of interface by-product can be generated, the increase of lithium anode interface impedance is caused.
Document (J.Mater.Chem.A, 2017,5,16984) passes through in lithium anode and solid electrolyte interface introducing
PEO base composite solid electrolyte, although improving interface compatibility, composite solid electrolyte lower lithium-ion electric at room temperature
Conductance limits the promotion of solid state battery high rate performance.Patent CN108923060A is made using lithium salts-acetonitrile solution of high concentration
For the interface-modifying layer of lithium anode and solid electrolyte, cathode/electrolyte interface ionic resistance is reduced, but due to second
Nitrile solvent itself is not sufficiently stable to lithium metal, is unfavorable for forming stable SEI film in metallic lithium surface, therefore be unfavorable for gold
Belong to the long-term circulation of lithium.Patent CN105914405A prepares full solid state polymer electricity using the ring-opening polymerisation of epoxy compounds original position
Xie Zhi uses epoxy compounds, lithium salts and additives for battery of liquid etc. for presoma, injects between battery positive/negative plate,
Then in a heated condition, in-situ polymerization is solidified into all solid state electrolyte and obtains all-solid-state battery.Although what the patent proposed
The modifying interface of lithium metal can also be used alone in method, remove certain lithium salts (such as difluoro list oxalic acid in the composition of raw materials of the patent
Lithium borate, hexafluoroarsenate lithium, double fluorine sulfimide lithiums) to form stable SEI film to metallic lithium surface helpful outer, used by
Various epoxy compounds, which form SEI film to metallic lithium surface stabilization, does not have particularly effective effect.
Summary of the invention
It is an object of the invention to for lithium anode surface physics contact in current high specific energy solid metallic lithium battery
The problem of cathode of lithium dendritic growth and interface impedance constantly increase in difference and solid state battery cyclic process, provides a kind of solid-state
High conductivity gel electrolyte buffer layer is formed in situ in metallic lithium surface in the modifying interface method of lithium battery lithium anode,
To effectively promote solid state lithium battery high rate performance and cycle life.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that: a kind of solid state lithium battery lithium anode
Modifying interface method, comprising the following steps:
(1) under room temperature, in the glove box full of argon gas, precursor solution is configured, precursor solution includes DOL molten
Agent, lithium salts, organic electrolysis solution additive, inorganic electrolyte solution additive；The volume ratio 3 of DOL solvent and organic electrolysis solution additive
20~30:1 of mass ratio of~5:1, DOL solvent and inorganic electrolyte solution additive, lithium salts mass fraction in entire precursor solution
Accounting is 12%~20%；
(2) lithium foil cathode is vertically impregnated in precursor solution, it is vertical later to take out, then lithium foil cathode is heated,
Make the DOL solvent in precursor solution in lithium salts LiAsF6Under the action of ring-opening polymerisation in situ occurs automatically, and in lithium foil cathode
Surface forms gel polymer electrolyte film；
(3) step (2) are iteratively repeated, make the gel polymer electrolyte thickness control of metallic lithium surface 0.8~
1.5um；
(4) by the lithium foil electrode of surface covering gel polymer electrolyte and the anode-solid electrolyte prepared
Layer fitting, gel polymer electrolyte is between lithium foil cathode and solid electrolyte.
The organic electrolysis solution additive is the mixture of one or both of FEC, VC.
The inorganic electrolyte solution additive is difluorine oxalic acid boracic acid lithium LiDFOB.
The lithium salts is LiAsF6、LiPF6One or both of mixture.
The lithium foil cathode is one or more of lithium metal, lithium-aluminium alloy, lithium boron alloy.
40 DEG C~70 DEG C of in-situ polymerization temperature, polymerization time 0.5h~1h.
The beneficial effects of the present invention are: the surface physics improved between metal lithium electrode and solid electrolyte contact, thus
Reduce interface impedance.Meanwhile stable SEI film can be formed in metallic lithium surface, be conducive to the circulation for promoting solid state lithium battery
Performance.
Detailed description of the invention
Fig. 1 Li-Li Symmetrical cells, 0.2mA/cm2, 1mAh/cm2Cycle charge-discharge curve (60 DEG C of constant temperature tests)；
Fig. 2 LiNi0.5Co0.2Mn0.3O2- Li solid state battery 0.1C circulation life curve (60 DEG C of constant temperature tests).
Specific embodiment
In order to further clearly illustrate the present invention, below by specific embodiment to the present invention further specifically
It is bright.
The modifying interface method of solid state lithium battery lithium anode of the invention, comprising the following steps:
(1) under room temperature, in the glove box full of argon gas, precursor solution is configured, precursor solution includes DOL molten
Agent, lithium salts, organic electrolysis solution additive, inorganic electrolyte solution additive；The volume ratio 3 of DOL solvent and organic electrolysis solution additive
20~30:1 of mass ratio of~5:1, DOL solvent and inorganic electrolyte solution additive, lithium salts mass fraction in entire precursor solution
Accounting is 12%~20%；
(2) lithium foil cathode is vertically impregnated in precursor solution, it is vertical later to take out, then lithium foil cathode is heated,
Make the DOL solvent in precursor solution in lithium salts LiAsF6Under the action of ring-opening polymerisation in situ occurs automatically, and in lithium foil cathode
Surface forms gel polymer electrolyte film；
(3) step (2) are iteratively repeated, make the gel polymer electrolyte thickness control of metallic lithium surface 0.8~
1.5um；
(4) by the lithium foil electrode of surface covering gel polymer electrolyte and the anode-solid electrolyte prepared
Layer fitting, gel polymer electrolyte is between lithium foil cathode and solid electrolyte.
The organic electrolysis solution additive is the mixture of one or both of FEC, VC.
The inorganic electrolyte solution additive is difluorine oxalic acid boracic acid lithium LiDFOB.
The lithium salts is LiAsF6、LiPF6One or both of mixture.
The lithium foil cathode is one or more of lithium metal, lithium-aluminium alloy, lithium boron alloy.
40 DEG C~70 DEG C of in-situ polymerization temperature, polymerization time 0.5h~1h.
The present invention realizes the surface modification of metal lithium electrode by the way of in-situ preparation gelatin polymer.The gel is poly-
In the presoma for closing object, 1,3 dioxolane solvents (DOL) comprising ring-opening polymerisation in situ can occur under lithium salts effect, together
When also include a variety of additives that stable SEI film can be formed to metallic lithium surface.Precursor solution passes through the side simply heated
On metal lithium electrode surface in-situ polymerization occurs for formula, and being formed, there is viscoelastic DOL oligomer to modify buffer layer, is effectively improved lithium
Electrode is contacted with the static state of solid-state electrolyte layer with the surface physics under dynamic condition, is conducive to solid state battery high rate performance and is played.
Simultaneously the SEI film for additive in precursor solution be very beneficial for metallic lithium surface formed it is uniform, stablize and high-intensitive
SEI film effectively inhibits the growth of metal Li dendrite and the interface side reaction effectively between barrier metal lithium and solid electrolyte,
Conducive to the performance of solid state lithium battery long circulating performance.In addition, being had very using the gel polymer electrolyte of this method preparation
High ionic conductivity (10-3S/cm), this is beneficial to transporting and the performance of battery high rate performance for lithium ion.
Embodiment 1
(1) under room temperature, in the glove box full of argon gas, precursor solution is prepared.Detailed process are as follows: glass beaker
Middle configuration mixed solvent DOL:FEC (fluorinated ethylene carbonate)=15ml:5ml, is separately added into the LiDFOB of 0.75g later,
3.72g LiAsF6, stir evenly.
(2) metallic lithium foil electrode is vertically impregnated in precursor solution, it is vertical later to take out, surface is hung with into presoma
The metallic lithium foil of solution is placed under infrared baking heat and heats, and heating and temperature control is at 40 degrees Celsius, heating time 0.5h, forerunner
DOL can be in LiAsF in liquid solution6Automatically ring-opening polymerisation in situ occurs under the action of salt, and forms 0.2~0.25um on lithium surface
The gel polymer electrolyte film of left and right.
(3) step 4 time in (2) repeatedly, make the gel polymer electrolyte thickness control of metallic lithium surface 0.9um~
1.0um.
(4) by the lithium foil electrode of surface covering gel polymer electrolyte and the anode-solid electrolyte prepared
Layer fitting, gel polymer electrolyte is between lithium metal and solid electrolyte.
Embodiment 2
(1) under room temperature, in the glove box full of argon gas, precursor solution is prepared.Detailed process are as follows: glass beaker
Middle configuration mixed solvent DOL:VC (vinylene carbonate)=25ml:5ml, is separately added into the LiDFOB of 0.84g, 7.39g later
LiPF6, stir evenly.
(2) metallic lithium foil electrode is vertically impregnated in precursor solution, it is vertical later to take out, surface is hung with into presoma
The metallic lithium foil of solution is placed under infrared baking heat and heats, and heating and temperature control waits 1h, precursor solution at 70 degrees Celsius
Middle DOL can be in LiAsF6Automatically ring-opening polymerisation in situ occurs under the action of salt, and forms 0.3~0.35um's or so on lithium surface
Gel polymer electrolyte film.
(3) step 4 time in (2) repeatedly, make the gel polymer electrolyte thickness control of metallic lithium surface 1.2~
1.4um。
(4) by the lithium foil electrode of surface covering gel polymer electrolyte and the anode-solid electrolyte prepared
Layer fitting, gel polymer electrolyte is between lithium metal and solid electrolyte.
Embodiment 3
(1) under room temperature, in the glove box full of argon gas, precursor solution is prepared.Detailed process are as follows: glass beaker
Middle configuration mixed solvent DOL:FEC (fluorinated ethylene carbonate)=20ml:5ml, is separately added into the LiDFOB of 0.8g, 1.0g later
LiFP6,3.5g LiAsF6, stir evenly.
(2) metallic lithium foil electrode is vertically impregnated in precursor solution, it is vertical later to take out, surface is hung with into presoma
The metallic lithium foil of solution is placed under infrared baking heat and heats, and heating and temperature control is preceding at 60 degrees Celsius, heating time 0.75h
DOL can be in LiFP in drive liquid solution6With LiAsF6Automatically ring-opening polymerisation in situ occurs under the collective effect of salt, and in lithium surface shape
At the gel polymer electrolyte film of 0.25~0.3um or so.
(3) step 4 time in (2) repeatedly, make the gel polymer electrolyte thickness control of metallic lithium surface 1um~
1.2um.
(4) by the lithium foil electrode of surface covering gel polymer electrolyte and the anode-solid electrolyte prepared
Layer fitting, gel polymer electrolyte is between lithium metal and solid electrolyte.
Embodiment 4
(1) under room temperature, in the glove box full of argon gas, precursor solution is prepared.Detailed process are as follows: glass beaker
Middle configuration mixed solvent DOL:FEC (fluorinated ethylene carbonate)=25ml:5ml, is separately added into the LiDFOB of 1.2g later, 5g's
LiFP6, 2.3g LiAsF6, stir evenly.
(2) metallic lithium foil electrode is vertically impregnated in precursor solution, it is vertical later to take out, surface is hung with into presoma
The metallic lithium foil of solution is placed under infrared baking heat and heats, and heating and temperature control is at 50 degrees Celsius, heating time 0.6h, forerunner
DOL can be in LiFP in liquid solution6With LiAsF6Automatically ring-opening polymerisation in situ occurs under the collective effect of salt, and is formed on lithium surface
The gel polymer electrolyte film of 0.3~0.35um or so.
(3) step 3 time in (2) repeatedly, make the gel polymer electrolyte thickness control of metallic lithium surface 0.9um~
1.05um。
(4) by the lithium foil electrode of surface covering gel polymer electrolyte and the anode-solid electrolyte prepared
Layer fitting, gel polymer electrolyte is between lithium metal and solid electrolyte.
By taking embodiment 1 as an example, as shown in Figure 1, assembly Li-Li Symmetrical cells, carry out constant current charge-discharge at 60 DEG C and follow
Ring test, current density 0.2mA/cm2, charge/discharge capacity is respectively 1mAh/cm2.Unmodified lithium electrode, from the 1st circle to the
In the cyclic process of 300 circles, battery polarization voltage is gradually increased, and the 300th reaches about 1000mV high value when enclosing；Surface modification
Lithium electrode, from the 1st circle to the 300th circle cyclic process in, polarization potential is relatively stable, and maintains lower value, about 150~
180mV.As shown in Fig. 2, assembly LiNi0.5Co0.2Mn0.3O2- Li solid state battery carries out the survey of cycle charge discharge electrical property at 60 DEG C
Examination, charge-discharge magnification 0.1C, 2.75~4.3V of charging/discharging voltage range.The solid state battery of unmodified lithium electrode assembly,
2nd circle circulation volume is about 150mAh/g, after circulation 120 times, capacity only residue 30mAh/g, and capacity retention ratio 20%.Through boundary
The solid state battery of the lithium electrode assembly of face modification, the 2nd circle circulation volume is about 155mAh/g, and after circulation 120 times, capacity is about
110mAh/g, capacity retention ratio 70.9%.
Embodiment described above is merely to illustrate technical idea and feature of the invention, in the art its object is to make
Technical staff it will be appreciated that the contents of the present invention and implement accordingly, patent model of the invention only cannot be limited with the present embodiment
It encloses, i.e., same changes or modifications made by all disclosed spirit are still fallen in the scope of the patents of the invention.
Claims (6)
1. a kind of modifying interface method of solid state lithium battery lithium anode, which comprises the following steps:
(1) under room temperature, full of argon gas glove box in, configure precursor solution, precursor solution include DOL solvent,
Lithium salts, organic electrolysis solution additive, inorganic electrolyte solution additive；The volume ratio 3~5 of DOL solvent and organic electrolysis solution additive:
20~30:1 of mass ratio of 1, DOL solvent and inorganic electrolyte solution additive, lithium salts mass fraction accounting in entire precursor solution
It is 12%~20%；
(2) lithium foil cathode is vertically impregnated in precursor solution, it is vertical later to take out, then lithium foil cathode is heated, before making
The DOL solvent in liquid solution is driven in lithium salts LiAsF6Under the action of ring-opening polymerisation in situ occurs automatically, and in lithium foil negative terminal surface
Form gel polymer electrolyte film；
(3) step (2) are iteratively repeated, make the gel polymer electrolyte thickness control of metallic lithium surface in 0.8~1.5um；
(4) the lithium foil electrode of surface covering gel polymer electrolyte is pasted with the anode-solid-state electrolyte layer prepared
It closes, gel polymer electrolyte is between lithium foil cathode and solid electrolyte.
2. the modifying interface method of solid state lithium battery lithium anode according to claim 1, which is characterized in that described organic
Electrolysis additive is the mixture of one or both of FEC, VC.
3. the modifying interface method of solid state lithium battery lithium anode according to claim 1, which is characterized in that described inorganic
Electrolysis additive is difluorine oxalic acid boracic acid lithium LiDFOB.
4. the modifying interface method of solid state lithium battery lithium anode according to claim 1, which is characterized in that the lithium salts
For LiAsF6、LiPF6One or both of mixture.
5. the modifying interface method of solid state lithium battery lithium anode according to claim 1, which is characterized in that the lithium foil
Cathode is one or more of lithium metal, lithium-aluminium alloy, lithium boron alloy.
6. the modifying interface method of solid state lithium battery lithium anode according to claim 1, which is characterized in that in-situ polymerization
40 DEG C~70 DEG C of temperature, polymerization time 0.5h~1h.
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|---|---|---|---|---|
| CN111082150A (en) * | 2019-12-20 | 2020-04-28 | 中国电子科技集团公司第十八研究所 | Interface modification method between electrolyte layer and lithium negative electrode in solid-state secondary lithium battery |
| CN111370627A (en) * | 2020-03-27 | 2020-07-03 | 中国人民解放军军事科学院防化研究院 | Direct compounding method of metal lithium electrode and inorganic solid electrolyte ceramic diaphragm |
| CN111509195A (en) * | 2020-05-07 | 2020-08-07 | 武汉理工大学 | Surface modification method for metal lithium cathode in all-solid-state lithium battery |
| CN111834662A (en) * | 2020-08-31 | 2020-10-27 | 珠海冠宇电池股份有限公司 | Interface functional layer, preparation method thereof and lithium ion battery |
| CN112072164A (en) * | 2020-08-28 | 2020-12-11 | 蜂巢能源科技有限公司 | Solid-state lithium battery and preparation method thereof |
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| CN113690485A (en) * | 2020-05-18 | 2021-11-23 | 北京理工大学 | Solid electrolyte interface film, alkali metal electrode and preparation method thereof |
| CN114242958A (en) * | 2021-12-21 | 2022-03-25 | 浙江大学 | Method for modifying lithium metal interface in sulfide solid-state battery and application |
| CN114300805A (en) * | 2021-12-02 | 2022-04-08 | 厦门大学 | All-solid-state battery with improved interface layer and electrode interface improvement method thereof |
| CN114583172A (en) * | 2022-03-07 | 2022-06-03 | 中南大学 | Artificial SEI material, SEI film, preparation method of SEI film and application of SEI film in metal lithium battery |
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| CN113690485A (en) * | 2020-05-18 | 2021-11-23 | 北京理工大学 | Solid electrolyte interface film, alkali metal electrode and preparation method thereof |
| CN113690485B (en) * | 2020-05-18 | 2023-12-22 | 北京理工大学 | Solid electrolyte interface film, alkali metal electrode and preparation method thereof |
| CN112072164A (en) * | 2020-08-28 | 2020-12-11 | 蜂巢能源科技有限公司 | Solid-state lithium battery and preparation method thereof |
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| CN112164778A (en) * | 2020-09-23 | 2021-01-01 | 长沙矿冶研究院有限责任公司 | Lithium cathode and preparation method thereof |
| CN112164778B (en) * | 2020-09-23 | 2022-04-15 | 长沙矿冶研究院有限责任公司 | Lithium cathode and preparation method thereof |
| CN112625592A (en) * | 2020-10-26 | 2021-04-09 | 上海汽车集团股份有限公司 | Preparation method of lithium metal interface modification layer |
| CN112615046A (en) * | 2020-11-27 | 2021-04-06 | 辽宁科技大学 | Method for in-situ regulation and control of solid electrolyte interface layer of lithium battery |
| CN112615046B (en) * | 2020-11-27 | 2023-11-21 | 辽宁科技大学 | Method for in-situ regulation and control of solid electrolyte interface layer of lithium battery |
| CN112820936A (en) * | 2021-01-07 | 2021-05-18 | 北京理工大学 | Metal lithium composite negative electrode based on inorganic solid electrolyte matrix and preparation method thereof |
| CN113422002A (en) * | 2021-07-28 | 2021-09-21 | 中汽创智科技有限公司 | Metallic lithium cathode, preparation method of metallic lithium cathode and application of metallic lithium cathode |
| CN114300805A (en) * | 2021-12-02 | 2022-04-08 | 厦门大学 | All-solid-state battery with improved interface layer and electrode interface improvement method thereof |
| CN114242958A (en) * | 2021-12-21 | 2022-03-25 | 浙江大学 | Method for modifying lithium metal interface in sulfide solid-state battery and application |
| CN114583172A (en) * | 2022-03-07 | 2022-06-03 | 中南大学 | Artificial SEI material, SEI film, preparation method of SEI film and application of SEI film in metal lithium battery |
| CN114583172B (en) * | 2022-03-07 | 2023-12-15 | 中南大学 | Artificial SEI material, SEI film, preparation thereof and application thereof in metal lithium battery |
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