CN109360937A - A kind of cathode with SEI protective layer, preparation method and lithium/sodium metal battery - Google Patents
A kind of cathode with SEI protective layer, preparation method and lithium/sodium metal battery Download PDFInfo
- Publication number
- CN109360937A CN109360937A CN201811359622.8A CN201811359622A CN109360937A CN 109360937 A CN109360937 A CN 109360937A CN 201811359622 A CN201811359622 A CN 201811359622A CN 109360937 A CN109360937 A CN 109360937A
- Authority
- CN
- China
- Prior art keywords
- cathode
- protective layer
- sei
- lithium
- organic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of cathode with SEI protective layer, including cathode and the SEI protective layer for being compounded in negative terminal surface；The SEI protective layer includes inorganic phase and organic polymer phase；Inorganic phase concentration since the side of SEI protective layer contact cathode gradually decreases；Mutually concentration gradually rises the organic polymer since the side of SEI protective layer contact cathode；The inorganic phase includes compound or graphene oxide shown in Formulas I；R is Li or Na；M is one or more of Zn, In and Sn；The organic polymer is mutually one or more of polymethyl acrylate, dimethyl silicone polymer, polyethylene glycol oxide and polyether sulfone.Cathode in the present invention has the protective layer of two-phase laminated flow, while having the flexibility of polymer and the rigidity of alloy protecting layer, improves the stability and safety of cathode.The present invention also provides a kind of preparation method of cathode with SEI protective layer and lithium/sodium metal batteries.
Description
Technical field
The invention belongs to lithium/sodium metal battery technical field more particularly to a kind of cathode with SEI protective layer, its system
Preparation Method and lithium/sodium metal battery.
Background technique
Currently, by construct artificial SEI (solid-electrolyte interface) protective layer to lithium anode into
A kind of method that row protection has proven to effective lithium metal protection；This method can be divided into the artificial SEI of organic polymer
Protective layer, the artificial SEI protective layer of inorganic salts, alloy protecting layer etc..Its main foundation is by lithium anode surface structure
Lithium anode and electrolyte can be completely cut off the lithium ion conducting that come by building one layer, the protective layer of electronic isolation, so that
Lithium anode can prevent it from puncturing in cyclic process to avoid the growth that Li dendrite is corroded and inhibited by electrolyte
Diaphragm causes battery failure that firing accident even occurs.
The artificial SEI protective layer of organic polymer, this protective layer be by metallic lithium surface coating have certain lithium from
The stable polymerization protective layer of electron conductivity, such as: Kynoar (PVDF), dimethyl silicone polymer (PDMS), polycyclic oxygen second
Alkane (PEO), tetraethoxysilane (TEOS) etc., but since the lithium ion conductivity of organic polymer is all relatively low, it greatly increases
Interface impedance, meanwhile, the mechanical strength of organic polymer is poor, the branch generated with the increase of cycle-index, lithium metal
Crystalline substance can penetrate polymer protective layer, so that protective layer be made to fail.
The artificial SEI protective layer of inorganic salts by magnetron sputtering, atomic layer deposition or utilizes oxidation-reduction method, in metal
One layer of inorganic salts protective layer with high-lithium ion conductivity of cathode of lithium surface building, but the construction method of this kind of protective layer
Complexity, it is with high costs, and in electrochemistry cyclic process, with the variation of lithium anode surface volume, inorganic salts
Artificial SEI protective layer is often frangible, to crack, so that protective layer fails.
Alloy type lithium anode protective layer can be restored and further and golden by adding in the electrolytic solution by lithium metal
Belong to lithium to react the additive salt to form alloy or lithium metal is directly made to contact the solution containing the type salt, thus in metal
Lithium surface forms uniform alloy protecting layer.But alloy protecting layer is equally faced with as the cycle progresses, alloy protecting layer
The variation of interfacial volume can be led to the problem of to fragmentation.
Therefore, how simultaneously to solve the problems, such as that cathode SEI protective layer is easy to produce frangible caused by volume change, and mechanical
The low problem of intensity difference, lithium ion conductivity is the direction of this field research.
Summary of the invention
The purpose of the present invention is to provide a kind of cathode with SEI protective layer, preparation method and lithium/sodium metal electricity
Pond.Cathode while ionic conductivity with higher, excellent mechanical performance in the present invention, and the body at interface is effectively relieved
Product variation.
The present invention provides a kind of cathode with SEI protective layer, protects including cathode and the SEI for being compounded in negative terminal surface
Layer；
The SEI protective layer includes inorganic phase and organic polymer phase；
Inorganic phase concentration since the side of SEI protective layer contact cathode gradually decreases；The organic polymer phase
Concentration gradually rises since the side of SEI protective layer contact cathode；
The inorganic phase includes compound or graphene oxide shown in Formulas I；
RxMyFormulas I；
Wherein, R is Li or Na；M is one or more of Zn, In and Sn；
The organic polymer is mutually in polymethyl acrylate, dimethyl silicone polymer, polyethylene glycol oxide and polyether sulfone
It is one or more of.
Preferably, the SEI protective layer with a thickness of 10 μm.
Preferably, the mass fraction of inorganic phase is 16.65~50% in the SEI protective layer；
The mass fraction of organic polymer phase is 50~83.35% in the SEI protective layer.
The present invention provides a kind of preparation method of cathode with SEI protective layer, comprising the following steps:
A inorganic raw material and organic polymer are dissolved in a solvent), after ultrasonic treatment, obtain mixed solution；
The inorganic raw material is halide salt or graphene oxide；The halide salt is in zinc halide, indium halide and gallium halide
One or more；
The organic polymer is one in polymethyl acrylate, dimethyl silicone polymer, polyethylene glycol oxide and polyether sulfone
Kind is several；
B) under an inert atmosphere, negative terminal surface is contacted with the mixed solution, is reacted, obtained with SEI protection
The cathode of layer；
The cathode is lithium metal or metallic sodium.
Preferably, in the mixed solution, the mass fraction of inorganic matter is 0.5~7.5%.
Preferably, in the mixed solution, the mass fraction of organic polymer is 4~16%.
Preferably, the step B) in react temperature be 25~100 DEG C；
The step B) in react time be 20~120s.
Preferably, the step B) in contact of the cathode with mixed solution be following two:
1) cathode is placed in the mixed solution；
2) mixed solution is spin-coated on to the surface of the cathode.
The present invention provides a kind of lithium/sodium metal battery, which is characterized in that the cathode in the lithium/sodium metal battery is upper
With the cathode of SEI protective layer described in text.
The present invention provides a kind of cathode with SEI protective layer, protect including cathode and the SEI for being compounded in negative terminal surface
Layer；The SEI protective layer includes inorganic phase and organic polymer phase；The inorganic phase contacts the side of cathode from SEI protective layer
Start concentration to gradually decrease；Mutually concentration gradually rises the organic polymer since the side of SEI protective layer contact cathode；Institute
Stating inorganic phase includes compound or graphene oxide shown in Formulas I；RxMyFormulas I；Wherein, R is Li or Na；M is in Zn, In and Sn
It is one or more of；The organic polymer is mutually in polymethyl acrylate, dimethyl silicone polymer, polyethylene glycol oxide and polyether sulfone
One or more.Cathode in the present invention has the polymer and inorganic matter protective layer of two-phase laminated flow " cocktail " structure,
The protective layer has the flexibility (lithium metal/volume change of the sodium cathode in cyclic process can be effectively relieved) of polymer simultaneously
And inorganic matter such as alloy protecting layer rigidity (lithium metal/sodium cathode dendritic growth can be resisted, effectively prevent dendrite puncture every
Film), by the effect of this " coupling hardness with softness ", fully lithium metal/sodium cathode is protected, substantially increase lithium metal/
The stability and safety of sodium cathode.The experimental results showed that the ionic conductivity in this case invention is up to 1.759 × 10- 4Scm-1, and there is good cycle performance.
Preparation method in the present invention is novel, one-step method reaction in-situ can construct with the alloy mutually separated with polymerize
The lithium metal of object complex protection structure/sodium cathode；Preparation cost is cheap, and operating condition is simple, is not required to by other Preparation equipments；
And be swift in response, effectively obtain " cocktail " structure that there is polymer alloy mutually to separate.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the schematic diagram of reaction process in the present invention；
Fig. 2 is the structure and energy spectrum analysis figure of the cathode in the embodiment of the present invention 1 with SEI protective layer；
Fig. 3 is to have the cathode of SEI protective layer to electrode battery loop test figure in the embodiment of the present invention 1；
Fig. 4 is to have the cathode of SEI protective layer to electrode battery loop test figure in the embodiment of the present invention 3；
Fig. 5 is to have the cathode of SEI protective layer to electrode battery loop test figure in the embodiment of the present invention 15；
Fig. 6 is to have the cathode of SEI protective layer to electrode battery loop test figure in the embodiment of the present invention 21；
Fig. 7 is to have the cathode of SEI protective layer to electrode battery loop test figure in the embodiment of the present invention 27.
Specific embodiment
The purpose of the present invention is to provide a kind of cathode with SEI protective layer, including cathode and it is compounded in negative terminal surface
SEI protective layer；
The SEI protective layer includes inorganic phase and organic polymer phase；
Inorganic phase concentration since the side of SEI protective layer contact cathode gradually decreases；The organic polymer phase
Concentration gradually rises since the side of SEI protective layer contact cathode；
The inorganic phase includes compound or graphene oxide shown in Formulas I；
RxMyFormulas I；
Wherein, R is Li or Na；M is one or more of Zn, In and Sn；
The organic polymer is mutually in polymethyl acrylate, dimethyl silicone polymer, polyethylene glycol oxide and polyether sulfone
It is one or more of.
In the present invention, the cathode is preferably metal lithium sheet or metallic sodium piece；The thickness of the SEI protective layer is preferably
1~50 μm, more preferably 10~40 μm, most preferably 10~20 μm.
It include inorganic phase and organic polymer phase in the SEI protective layer, the inorganic phase contacts cathode from SEO protective layer
Side start concentration and gradually decrease；Mutually concentration is gradually since the side of SEI protective layer contact cathode for the organic polymer
It increases.Since the organic polymer of ionic conduction can mutually provide higher flexible and ionic conductivity, and lower layer (bears with described
The side of pole surface contact) the higher alloy of concentration Young's modulus mutually with higher and lithium ion conductivity, it can be effectively
Prevent dendritic growth from puncturing protective layer.
In the present invention, in the SEI protective layer, the mass fraction of inorganic matter phase is preferably 16.65~50%, more preferably
Be 28.5~37.5%, specifically, in an embodiment of the present invention, can be 16.5%, 28.5%, 33.3%, 37.5% or
50%；The mass fraction of the organic polymer phase is preferably 50~83.35%, and more preferably 62.5~71.5%, specifically,
In an embodiment of the present invention, it can be 83.5%, 71.5%, 62.5%, 66.7% or 50%.
In the present invention, the inorganic phase can be graphene oxide, or the chemical combination with chemical formula shown in Formulas I
Object；
RxMyFormulas I；
Wherein, R is Li or Na；M is one or more of Zn, In and Sn.
The organic polymer is mutually in polymethyl acrylate, dimethyl silicone polymer, polyethylene glycol oxide and polyether sulfone
It is one or more of.
The present invention also provides a kind of preparation methods of cathode with SEI protective layer, comprising the following steps:
A inorganic raw material and organic polymer are dissolved in a solvent), after ultrasonic treatment, obtain mixed solution；
The inorganic raw material is halide salt or graphene oxide；The halide salt is in zinc halide, indium halide and gallium halide
One or more；
The organic polymer is one in polymethyl acrylate, dimethyl silicone polymer, polyethylene glycol oxide and polyether sulfone
Kind is several；
B) under an inert atmosphere, cathode is contacted with the mixed solution, is reacted, obtain that there is SEI protective layer
Cathode；
The cathode is lithium metal or metallic sodium.
The present invention dissolves inorganic raw material with organic polymer in a solvent, successively carries out ultrasonic treatment and vacuum defoamation,
Obtain evenly dispersed mixed solution.
The inorganic raw material is halide salt or graphene oxide；The halide salt is in zinc halide, indium halide and gallium halide
One or more；The solvent is preferably that N-methyl pyrrolidones, n,N-dimethylacetamide, tetrahydrofuran and dimethyl are sub-
One or more of sulfone；The type of the organic polymer is consistent with the type of above-mentioned organic polymer, and details are not described herein.
In the mixed solution, the mass fraction of the inorganic matter is preferably 0.5~7.5%, and more preferably 2~6%,
Specifically, in an embodiment of the present invention, can be 2%, 4% or 6%.The mass fraction of the organic polymer is preferably 4
~16%, more preferably 4~10%.
In the present invention, the frequency of the ultrasound is preferably 20~60KHz, more preferably 40~50KHz；The ultrasound
Time is preferably 1~10 hour, and the temperature of more preferably 3~8 hours, most preferably 5~6 hours, the ultrasound is preferably 30
~70 DEG C, more preferably 50~60 DEG C.The present invention does not have special limitation to the vacuum defoamation, using those skilled in the art
The technology of common vacuum defoamation.
After obtaining mixed solution, the present invention contacts negative terminal surface with the mixed solution, is reacted, is had
The cathode of SEI protective layer.
The present invention is preferably existing to carry out cleaning pretreatment for the negative electrode material: the surface of negative electrode tab is carried out clearly using acetone
It washes, removes surface impurity, dry spare.
In the present invention, there are mainly two types of the modes that the negative terminal surface is contacted with mixed solution, first is that the contact that suspends is anti-
Negative electrode tab is placed in mixed solution by Ying Fa, due to the lithium piece or sodium piece that negative electrode tab is low-density, be placed in mixed solution
Afterwards, negative electrode tab can swim in the surface of mixed solution；Another kind is spin-coating method.
Mixed solution is contacted with negative electrode tab surface to be reacted, and the halide salt or graphene oxide in mixed solution are in metal
Under the effect of lithium/sodium strong reducing property, starts mobile to the interface of close lithium metal/sodium and be enriched with, at lithium metal/sodium interface
The ionizable metal salt (such as Sn ion) at place is reduced into tin simple substance and further forms high-lithium ion conduction velocity with lithium metal/sodium
Lithium-tin alloy, ultimately form a kind of protective layer of " cocktail " structure that polymer phase disperses with two phase gradient of alloy phase.
The present invention preferably carries out above-mentioned reaction under an inert atmosphere, and the inert atmosphere is oxygen content < 0.1ppm, and water contains
Amount < 0.1ppm；The temperature of the reaction is preferably 25~100 DEG C, more preferably 30~80 DEG C, most preferably 40~60 DEG C；Institute
The time for stating reaction is preferably 20~120s, more preferably 20~100s, most preferably 20~50s.
The present invention provides a kind of cathode with SEI protective layer, protect including cathode and the SEI for being compounded in negative terminal surface
Layer；The SEI protective layer includes inorganic phase and organic polymer phase；The inorganic phase contacts the side of cathode from SEI protective layer
Start concentration to gradually decrease；Mutually concentration gradually rises the organic polymer since the side of SEI protective layer contact cathode；Institute
Stating inorganic phase includes compound or graphene oxide shown in Formulas I；RxMyFormulas I；Wherein, R is Li or Na；M is in Zn, In and Sn
It is one or more of；The organic polymer is mutually in polymethyl acrylate, dimethyl silicone polymer, polyethylene glycol oxide and polyether sulfone
One or more.Cathode in the present invention has the polymer and inorganic matter protective layer of two-phase laminated flow " cocktail " structure,
The protective layer has the flexibility (lithium metal/volume change of the sodium cathode in cyclic process can be effectively relieved) of polymer simultaneously
And inorganic matter such as alloy protecting layer rigidity (lithium metal/sodium cathode dendritic growth can be resisted, effectively prevent dendrite puncture every
Film), by the effect of this " coupling hardness with softness ", fully lithium metal/sodium cathode is protected, substantially increase lithium metal/
The stability and safety of sodium cathode.The experimental results showed that the ionic conductivity in this case invention is up to 1.759 × 10- 4Scm-1；And there is good cycle performance.
In order to further illustrate the present invention, with reference to embodiments to provided by the invention a kind of with SEI protective layer
Cathode, preparation method, that is, lithium/sodium metal battery are described in detail, but cannot be understood as to the scope of the present invention
It limits.
Embodiment 1
Weigh two hydrated stannous chloride (SnCl2·2H2O), 100mg；Kynoar-hexafluoropropene polymer (PVDF-
HFP), 500mg；It is dissolved in the solution that N-methyl pyrrolidones is made into 5g, is stirred 5 hours at room temperature, so that Kynoar-hexafluoro
Acrylic polymers sufficiently dissolves, then is placed in ultrasound 5 hours in ultrasound, disperses inorganic salts polymer more in blend solution
Add uniformly, obtains solution A.
(oxygen content < 0.1ppm, water content < 0.1ppm) will clear up the lithium metal on surface with acetone under an inert atmosphere
Piece/sodium piece (thickness: 600 μm, diameter: 16 millimeters) it puts down gently in solution surface, metal lithium sheet is suspended in solution surface and is reacted
For 20 seconds, surface becomes uniform dark gray from bright metallochrome；Reaction process schematic diagram is as shown in Figure 1；
Metal lithium sheet after reaction is sucked into extra solution with dust-free paper, is statically placed in glove box and dries, since tin can
To be restored to obtain metallic tin by the lithium metal of strong reducing property in metallic lithium surface, metallic tin further forms high lithium with lithium metal
The lithium-tin alloy of ionic conductance rate, to obtain having the lithium metal of two phase gradient of alloy polymers dispersion double shielding negative
Pole, protective layer thickness are 10 μm,
The structure and energy spectrum analysis of the obtained lithium anode with the dispersion double shielding of two phase gradient of alloy polymers
As shown in Figure 2；1. for the lithium anode cross-sectional scans figure of organic polymer alloy composite layer protection；2. being closed for organic polymer
Golden complex protection lithium anode surface scan figure；3. protecting the optics of lithium anode to shine for organic polymer alloy composite layer
Piece；4. being the cross-sectional scans figure of organic polymer alloy composite protection layer；5. for cutting for organic polymer alloy composite protection layer
The energy spectrum analysis of face fluorine element distribution；6. the power spectrum point being distributed for the section tin element of organic polymer alloy composite protection layer
Analysis.Region it can be seen from 5. and 6. between two dotted lines indicates SEI protective film, and the dotted line of lower section indicates and cathode contact
Side, arrow direction indicates the incremental direction of constituent content, and from top to bottom concentration is incremented by successively for metal tin element, and representing has
The fluorine element of machine polymer phase is incremented by successively from the bottom to top, it was demonstrated that the SEI protective layer in the present embodiment forms alloy phase and gathers
Close the gradient distribution of object phase.
In 5mAcm-2, 1mAh cm-2Under the conditions of, it is carried out with the lithium anode and pure metal lithium piece of the protection of homozygous layer gold
Electrode battery loop test is compared, as a result as shown in figure 3, when initial cycle starts, untreated pure metal lithium piece polarization is bright
It is aobvious, it is because surface free is handled, there are the impurity such as many defects and lithia, lithium carbonate；Pure alloy protecting lithium metal tool
There is polarizing voltage more smaller than alloy polymers complex protection metal lithium electrode, is the polymer because of complex protection layer surface
Ionic conductivity is lower than pure lithium-tin alloy before starting as activation；With the increase of charge and discharge number, pure metal lithium piece
Polarizing voltage starts to change from small to big and finally surge, and indicates that the dead lithium layer accumulation of metal lithium sheet pole piece after being recycled to the 60th circle is led
It causes internal resistance to sharply increase and short circuit has occurred；The lithium anode of pure lithium-tin alloy protection is after stablizing 100 circle of circulation, polarizing voltage
It begins to ramp up, shows homozygous golden protective layer as cyclical stability is deteriorated, lithium metal starts nonuniform deposition, and the dead lithium in surface increases
Thickness, Li dendrite start to grow, until short circuit occurs for battery；And alloy polymers protective layer is as the cycle progresses, protective layer is living
After change, voltage polarizing reduces, and keeps stable, even if in 5mA cm-2Extreme currents under, the compound guarantor of alloy polymers
The lithium anode of shield also shows excellent ionic conductance and interface stability.
According to the method in embodiment 1, successively using the halide salt and type of polymer and proportion in table 1, it is prepared into
To SEI protective layer.
The mass fraction of halide salt and polymer in 1 mixed solution of table
It is 5mA cm in current density-2, capacity is 1mAh cm-2In the case where, (the code name PFSI- of testing example 3
106) it, is obtained in embodiment 15 (code name PZI-106), embodiment 21 (code name PBI-106) and embodiment 27 (code name PII-106)
SEI protective film to electrode stability loop test curve；As a result as also shown in e.g. figs. 4-7.In 5mA it can be seen from Fig. 4~7
cm-2High current density under, the lithium anode protected by polymer alloy composite layer can steadily recycle 500 circles or more,
Reflect the excellent stability of shielded lithium anode and cycle performance.
Test embodiment 3 (code name PFSI-106), embodiment 15 (code name PZI-106), (the code name PBI- of embodiment 21
106) as a result as follows with ionic conductivity of the SEI protective film at 25 DEG C obtained in embodiment 27 (code name PII-106):
SnCl in embodiment 32The LiSn alloy SEI protective film ionic conductivity formed with lithium is 1.759 × 10- 4Scm-1；
ZnCl in embodiment 152It is 4.7 × 10 with the LiZn alloy SEI protective film ionic conductivity that lithium is formed-8Scm-1；
BiCl in embodiment 213It is 3.0 × 10 with the LiBi alloy SEI protective film ionic conductivity that lithium is formed-6Scm-1；
InCl in embodiment 273It is 5 × 10 with the LiIn alloy SEI protective film ionic conductivity that lithium is formed-6Scm-1。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of cathode with SEI protective layer, including cathode and the SEI protective layer for being compounded in negative terminal surface；
The SEI protective layer includes inorganic phase and organic polymer phase；
Inorganic phase concentration since the side of SEI protective layer contact cathode gradually decreases；The organic polymer is mutually from SEI
The side of protective layer contact cathode starts concentration and gradually rises；
The inorganic phase includes compound or graphene oxide shown in Formulas I；
RxMyFormulas I；
Wherein, R is Li or Na；M is one or more of Zn, In and Sn；
The organic polymer is mutually one of polymethyl acrylate, dimethyl silicone polymer, polyethylene glycol oxide and polyether sulfone
Or it is several.
2. cathode according to claim 1, which is characterized in that the SEI protective layer with a thickness of 10 μm.
3. cathode according to claim 1, which is characterized in that the mass fraction of inorganic phase is in the SEI protective layer
16.65~50%；
The mass fraction of organic polymer phase is 50~83.35% in the SEI protective layer.
4. a kind of preparation method of the cathode with SEI protective layer, comprising the following steps:
A inorganic raw material and organic polymer are dissolved in a solvent), after ultrasonic treatment, obtain mixed solution；
The inorganic raw material is halide salt or graphene oxide；The halide salt is one in zinc halide, indium halide and gallium halide
Kind is several；
The organic polymer be one of polymethyl acrylate, dimethyl silicone polymer, polyethylene glycol oxide and polyether sulfone or
It is several；
B) under an inert atmosphere, negative terminal surface is contacted with the mixed solution, is reacted, obtain that there is SEI protective layer
Cathode；
The cathode is lithium metal or metallic sodium.
5. the preparation method according to claim 4, which is characterized in that in the mixed solution, the mass fraction of inorganic matter
It is 0.5~7.5%.
6. the preparation method according to claim 4, which is characterized in that in the mixed solution, the quality of organic polymer
Score is 4~16%.
7. the preparation method according to claim 4, which is characterized in that the step B) in react temperature be 25~100
℃；
The step B) in react time be 20~120s.
8. according to the method described in claim 4, the it is characterized in that, step B) in contact of the cathode with mixed solution be with
Lower two kinds:
1) cathode is placed in the mixed solution；
2) mixed solution is spin-coated on to the surface of the cathode.
9. a kind of lithium/sodium metal battery, which is characterized in that the cathode in the lithium/sodium metal battery is appointed for claims 1 to 3
Have made from preparation method described in cathode or claim 4~8 any one described in meaning one with SEI protective layer
The cathode of SEI protective layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811359622.8A CN109360937A (en) | 2018-11-15 | 2018-11-15 | A kind of cathode with SEI protective layer, preparation method and lithium/sodium metal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811359622.8A CN109360937A (en) | 2018-11-15 | 2018-11-15 | A kind of cathode with SEI protective layer, preparation method and lithium/sodium metal battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109360937A true CN109360937A (en) | 2019-02-19 |
Family
ID=65345255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811359622.8A Pending CN109360937A (en) | 2018-11-15 | 2018-11-15 | A kind of cathode with SEI protective layer, preparation method and lithium/sodium metal battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109360937A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110380003A (en) * | 2019-07-02 | 2019-10-25 | 天津大学 | A kind of cathode of lithium battery and preparation method thereof, lithium battery |
| CN110993929A (en) * | 2019-11-22 | 2020-04-10 | 欣旺达电动汽车电池有限公司 | Polymer protective film, metal negative electrode material, lithium ion battery and preparation method |
| CN111029523A (en) * | 2019-12-10 | 2020-04-17 | 北京中科惠景储能材料科技有限公司 | Preparation method of high-stability artificial solid electrolyte interface membrane material |
| CN111509201A (en) * | 2020-03-20 | 2020-08-07 | 合肥国轩高科动力能源有限公司 | Preparation method of low direct current internal resistance positive electrode slurry |
| CN111600025A (en) * | 2020-04-23 | 2020-08-28 | 同济大学 | Zinc cathode material with elastic protective layer and preparation and application thereof |
| CN113206213A (en) * | 2021-04-29 | 2021-08-03 | 中国科学院宁波材料技术与工程研究所 | Silicon-based composite electrode and preparation method and application thereof |
| CN113346051A (en) * | 2021-06-04 | 2021-09-03 | 天津中电新能源研究院有限公司 | Preparation method of metal lithium surface protection layer |
| CN113437297A (en) * | 2020-03-23 | 2021-09-24 | 比亚迪股份有限公司 | Metallic lithium negative electrode, preparation method thereof and lithium battery |
| CN113764822A (en) * | 2021-09-09 | 2021-12-07 | 武汉科技大学 | High-ionic-conductivity composite coating film for lithium primary battery and preparation method thereof |
| CN114784259A (en) * | 2022-05-28 | 2022-07-22 | 浙江锋锂新能源科技有限公司 | Lithium metal battery cathode material, preparation method thereof and lithium metal battery |
| WO2022163125A1 (en) * | 2021-01-26 | 2022-08-04 | 株式会社Ｇｓユアサ | Nonaqueous electrolyte power storage element, power storage device, and method for producing nonaqueous electrolyte power storage element |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090111031A1 (en) * | 2007-10-31 | 2009-04-30 | Sony Corporation | Anode active material, anode, and battery |
| CN102315420A (en) * | 2010-07-05 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Metal cathode structure with protection layer and preparation method thereof |
| CN102881862A (en) * | 2011-07-12 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | Protective metal anode structure and preparation method thereof |
| CN105845891A (en) * | 2016-05-13 | 2016-08-10 | 清华大学 | Metal lithium negative electrode with dual-layer structure |
| CN107078251A (en) * | 2014-10-24 | 2017-08-18 | 株式会社Lg化学 | Secondary battery separator and its manufacture method including inorganic composite porous layer |
| CN107123788A (en) * | 2017-03-30 | 2017-09-01 | 中国科学院青岛生物能源与过程研究所 | A kind of lithium anode with organic-inorganic duplicate protection layer |
| CN107221649A (en) * | 2016-03-21 | 2017-09-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Electrode, its preparation method and application with Organic-inorganic composite protective layer |
| CN108365178A (en) * | 2018-02-11 | 2018-08-03 | 珠海光宇电池有限公司 | A kind of guard method of lithium an- ode, lithium an- ode and lithium battery |
| CN108511708A (en) * | 2018-03-14 | 2018-09-07 | 清华大学 | A kind of solid composite metal cathode of lithium |
| CN108796504A (en) * | 2018-01-19 | 2018-11-13 | 苏州大学 | A kind of preparation method of 3-dimensional metal cathode |
-
2018
- 2018-11-15 CN CN201811359622.8A patent/CN109360937A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090111031A1 (en) * | 2007-10-31 | 2009-04-30 | Sony Corporation | Anode active material, anode, and battery |
| CN102315420A (en) * | 2010-07-05 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Metal cathode structure with protection layer and preparation method thereof |
| CN102881862A (en) * | 2011-07-12 | 2013-01-16 | 中国科学院上海硅酸盐研究所 | Protective metal anode structure and preparation method thereof |
| CN107078251A (en) * | 2014-10-24 | 2017-08-18 | 株式会社Lg化学 | Secondary battery separator and its manufacture method including inorganic composite porous layer |
| CN107221649A (en) * | 2016-03-21 | 2017-09-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Electrode, its preparation method and application with Organic-inorganic composite protective layer |
| CN105845891A (en) * | 2016-05-13 | 2016-08-10 | 清华大学 | Metal lithium negative electrode with dual-layer structure |
| CN107123788A (en) * | 2017-03-30 | 2017-09-01 | 中国科学院青岛生物能源与过程研究所 | A kind of lithium anode with organic-inorganic duplicate protection layer |
| CN108796504A (en) * | 2018-01-19 | 2018-11-13 | 苏州大学 | A kind of preparation method of 3-dimensional metal cathode |
| CN108365178A (en) * | 2018-02-11 | 2018-08-03 | 珠海光宇电池有限公司 | A kind of guard method of lithium an- ode, lithium an- ode and lithium battery |
| CN108511708A (en) * | 2018-03-14 | 2018-09-07 | 清华大学 | A kind of solid composite metal cathode of lithium |
Non-Patent Citations (1)
| Title |
|---|
| YANG ZHAO ETAL: "Inorganic−Organic Coating via Molecular Layer Deposition Enables Long Life Sodium Metal Anode", 《NANO LETTERS》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110380003A (en) * | 2019-07-02 | 2019-10-25 | 天津大学 | A kind of cathode of lithium battery and preparation method thereof, lithium battery |
| CN110380003B (en) * | 2019-07-02 | 2022-08-30 | 天津大学 | Lithium battery cathode, preparation method thereof and lithium battery |
| CN110993929A (en) * | 2019-11-22 | 2020-04-10 | 欣旺达电动汽车电池有限公司 | Polymer protective film, metal negative electrode material, lithium ion battery and preparation method |
| CN110993929B (en) * | 2019-11-22 | 2021-05-07 | 欣旺达电动汽车电池有限公司 | Polymer protective film, metal negative electrode material, lithium ion battery and preparation method |
| CN111029523A (en) * | 2019-12-10 | 2020-04-17 | 北京中科惠景储能材料科技有限公司 | Preparation method of high-stability artificial solid electrolyte interface membrane material |
| CN111509201A (en) * | 2020-03-20 | 2020-08-07 | 合肥国轩高科动力能源有限公司 | Preparation method of low direct current internal resistance positive electrode slurry |
| CN113437297B (en) * | 2020-03-23 | 2022-10-18 | 比亚迪股份有限公司 | Metallic lithium negative electrode, preparation method thereof and lithium battery |
| CN113437297A (en) * | 2020-03-23 | 2021-09-24 | 比亚迪股份有限公司 | Metallic lithium negative electrode, preparation method thereof and lithium battery |
| CN111600025A (en) * | 2020-04-23 | 2020-08-28 | 同济大学 | Zinc cathode material with elastic protective layer and preparation and application thereof |
| WO2022163125A1 (en) * | 2021-01-26 | 2022-08-04 | 株式会社Ｇｓユアサ | Nonaqueous electrolyte power storage element, power storage device, and method for producing nonaqueous electrolyte power storage element |
| CN113206213A (en) * | 2021-04-29 | 2021-08-03 | 中国科学院宁波材料技术与工程研究所 | Silicon-based composite electrode and preparation method and application thereof |
| CN113346051A (en) * | 2021-06-04 | 2021-09-03 | 天津中电新能源研究院有限公司 | Preparation method of metal lithium surface protection layer |
| CN113764822A (en) * | 2021-09-09 | 2021-12-07 | 武汉科技大学 | High-ionic-conductivity composite coating film for lithium primary battery and preparation method thereof |
| CN114784259A (en) * | 2022-05-28 | 2022-07-22 | 浙江锋锂新能源科技有限公司 | Lithium metal battery cathode material, preparation method thereof and lithium metal battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109360937A (en) | A kind of cathode with SEI protective layer, preparation method and lithium/sodium metal battery | |
| Wu et al. | Tough gel electrolyte using double polymer network design for the safe, stable cycling of lithium metal anode | |
| CN106340616B (en) | A kind of cathode of lithium and preparation method thereof with sandwich structure for lithium battery | |
| Park et al. | Passivating ability of surface film derived from vinylene carbonate on tin negative electrode | |
| US20140220439A1 (en) | Composite protective layer for lithium metal anode and method of making the same | |
| CN108011079A (en) | A kind of surface modification method of lithium anode and application | |
| CN108767263B (en) | Preparation method and application of modified metal lithium negative electrode copper foil current collector | |
| CN109786675A (en) | Interface modification method for metal lithium cathode of solid-state lithium battery | |
| CN1365524A (en) | Magnesium-based (primary non-rechargeabel) and secondary (rechargeable) batteries | |
| CN108711609B (en) | Lithium metal negative electrode surface treatment process and application thereof | |
| CN110931875B (en) | Butadinitrile-based electrolyte coupling organic lithium salt and fluoroethylene carbonate, preparation method and application thereof | |
| CN107394176B (en) | Silicon-carbon composite material, preparation method and application thereof, and lithium ion battery cathode material | |
| Jang et al. | Surface coating layer on Li metal for increased cycle stability of Li–O2 batteries | |
| Croce et al. | The lithium polymer electrolyte battery IV. Use of composite electrolytes | |
| CN109585919B (en) | Lithium ion battery and electrolyte thereof | |
| CN109638255A (en) | A kind of alkali metal negative terminal surface in-situ treatment method and its application | |
| Kumar et al. | Electrochemical characterization of a zinc-based gel-polymer electrolyte and its application in rechargeable batteries | |
| CN109326798A (en) | A kind of preparation method and application for lithium anode protective layer | |
| JP3312836B2 (en) | Non-aqueous electrolyte secondary battery | |
| CN110148774A (en) | Nickelic tertiary cathode material system battery electrolytic solution and lithium ion battery | |
| CN107305963A (en) | Electrolyte for lithium-sulfur cell and preparation method thereof | |
| CN113314773A (en) | Aqueous zinc ion battery electrolyte and preparation method and application thereof | |
| CN108878890A (en) | A kind of lithium ion battery conductive film/lithium metal/conducting base three-decker combination electrode and preparation method thereof | |
| CN109742351A (en) | A kind of preparation method and application of in-stiu coating lithium titanate cathode material | |
| CN110911662A (en) | Lithium cathode with protective layer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190219 |