CN108400316A - Selfreparing oxidation film coats Na-K liquid alloy electrodes and its preparation method and application - Google Patents
Selfreparing oxidation film coats Na-K liquid alloy electrodes and its preparation method and application Download PDFInfo
- Publication number
- CN108400316A CN108400316A CN201810140846.3A CN201810140846A CN108400316A CN 108400316 A CN108400316 A CN 108400316A CN 201810140846 A CN201810140846 A CN 201810140846A CN 108400316 A CN108400316 A CN 108400316A
- Authority
- CN
- China
- Prior art keywords
- conductive carrier
- selfreparing
- oxidation film
- preparation
- karat gold
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
-
- 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
Na K liquid alloy electrodes and preparation method thereof are coated the invention discloses a kind of efficient selfreparing oxidation film and as the application of cathode; under inert gas protection; karat gold is belonged to and Na metals heat respectively; until fusing; conductive carrier is contacted with metal again; molten metal slowly moistens conductive carrier, is cooled to room temperature the conductive carrier for respectively obtaining load karat gold category and Na metals；The method for stacking alloying by physics, the selfreparing oxidation film that preparation structure is stablized at room temperature coat Na K liquid alloy electrodes.The selfreparing oxidation film for the Na K liquid alloys and surface that the electrode includes conductive carrier, is adsorbed on carrier.Electrode of the present invention has the characteristics that high coulombic efficiency, without dendritic growth and stable structure, can be used as potassium metal negative electrode and sodium metal negative electrode simultaneously, when being matched with the positive electrodes such as sulphur, Prussian blue, significantly improve the energy density and cyclical stability of full battery.
Description
Technical field
The present invention relates to alkali metal secondary battery negative material technical fields, and in particular to a kind of selfreparing oxidation film cladding
Na-K liquid alloy electrodes and preparation method thereof and as alkali metal secondary battery negative material application.
Background technology
Universal with new-energy automobile and mobile electronic device, there is an urgent need to develop height ratio capacity, high security, length to follow
Ring service life, inexpensive battery.Alkali metal secondary battery as a kind of new type of energy storage device, have large storage capacity, manufacturing cost it is low,
The features such as electrochemical window mouth width, has broad application prospects in fields such as mobile communication, electric vehicle and energy storage.Wherein alkali
Metal negative electrode has higher specific capacity relative to carbon material, metal oxide etc., but alkali metal cathode holds in use
It is also easy to produce dendrite, leads to battery short circuit, causes security risk.Branch can be completely inhibited by the liquid alloy of representative of Na-K alloys
Brilliant growth, becomes emerging no dendrite electrode material research direction.However Na-K liquid alloy surface tension is big, it is difficult to collect
Flow surface moistens, and seriously hinders its commercial applications.Therefore, the liquid metal electrode that research room temperature lower structure is stablized is to alkali gold
The application development for belonging to secondary cell is of great significance.
Research shows that Na-K liquid alloys are extremely potential high-performance without dendrite electrode material, have hypotoxicity,
The characteristics such as wide equilibrium temperature (all existing in liquid form for even -12.6 DEG C at normal temperatures).To obtain the Na-K liquid of stable structure
State alloy electrode needs to solve the problems, such as following (as shown in Figure 1)：1) Na-K liquid alloys difficulty is molded, Na-K alloy surfaces
Power is big, it is difficult to be moistened in collection liquid surface, and because of the form of its liquid, have certain mobility, it is difficult to form fixed shape
State；2) Na-K liquid alloys electrode and electrolyte interface are unstable, and Na-K liquid alloys are easy to fall off from electrode surface, are being electrolysed
Free liquid metal is formed in liquid, leads to the boundary for being difficult to maintain to be stabilized between Na-K liquid alloys electrode and electrolyte
The voltage fluctuation during circulating battery is caused in face.
Studies have shown that high-temperature process (>420 DEG C) wettability of the Na-K liquid alloys on carbon paper can be promoted, and meanwhile it is more
Pore structure substrate can capture more Na-K liquid alloys, solve the problems, such as Na-K liquid alloy mobility.However in room temperature
Under, due to the recovery of Na-K liquid alloy surface tension, causes the Na-K liquid alloys of combination electrode surface exposure to fall off, show
Simple carbon carrier load Na-K liquid alloys cannot inherently solve the problems, such as interface stability this.
At present both at home and abroad still without studying for stablizing Na-K liquid alloys electrode and electrolyte interface, both at home and abroad for
Na-K liquid alloy shuttle problems do not have any resolution policy.Therefore, it is Na-K to build stable electrode and electrolyte interface
Liquid alloy cathode large-scale application continues the critical problem solved.
Invention content
For the problems in background technology, the purpose of the present invention is to provide a kind of efficient selfreparing oxidation films to coat Na-K
Liquid alloy electrode and preparation method thereof and application as alkali metal secondary battery negative material, this method can be directly each
Structure selfreparing oxidation film coats Na-K liquid alloys on the conductive carrier of kind structure and type, has compared with strong stability to prepare
Property without dendrite alkali metal battery cathode.
A kind of preparation method of efficient selfreparing oxidation film cladding Na-K liquid alloy electrodes, includes the following steps：
1) under inert gas protection, karat gold is belonged to and being heated, until fusing, then conductive carrier and the karat gold category of fusing are connect
It touches, the karat gold of fusing belongs to slowly moistening conductive carrier, and after all absorbing, the conductive carrier that load karat gold belongs to is obtained after cooling；
Under inert gas protection, by Na METAL HEATING PROCESSs, until melting, then conductive carrier and the Na metals of fusing are connect
It touches, the Na metals of fusing slowly moisten conductive carrier, and after all absorbing, the conductive carrier of load Na metals is obtained after cooling；
2) under inert gas protection, by the conductive carrier of load karat gold category of step 1) preparation and leading for load Na metals
Charge carrier physics stacks, and karat gold category and the metallic alloying reactions of Na occurs, and generate oxidation film simultaneously, obtains selfreparing oxidation film
Coat Na-K liquid alloy electrodes；
Alternatively, infiltrating the conductive carrier of conductive carrier and load Na metals that load karat gold prepared by step 1) belongs in electricity
It solves in liquid, and stacks, alloying reaction occurs, and generate selfreparing oxidation film simultaneously, obtain selfreparing oxidation film and coat Na-K
Liquid alloy electrode.
In step 1), the conductive carrier can be various dimension conductive carriers, can be film, block from structural point
Shape body, powder etc. can be macromolecule, metal, metal oxide, metal organic frame, carbon material etc. from material angle.It is preferred that
For certain thickness two-dimensional film conductive carrier, most preferably the two-dimensional film carbon material of certain thickness and area.
The carbon material can be quantum dot, carbon pipe, multi wall carbon pipe, carbon fiber, graphene, graphene roll, carbon array,
Vertical graphene, carbon cloth, mesoporous carbon, hollow ball, multi-layer hollow, nano flower, biomass carbon material etc..The conductive carrier
Material can be the compound of multiple material.The carbon material can be hard carbon and soft carbon.
Further preferably, the conductive carrier is carbon cloth.
The thickness of the conductive carrier is 0.1mm~10mm, further preferably 0.5mm~5mm, most preferably 1mm
~2mm.
The area of the conductive carrier is 0.1cm2~10cm2, further preferably 0.2cm2~2cm2, most preferably
0.5cm2~1.5cm2, wherein length and width shape is unlimited, is preferably square or round.
In step 1), the karat gold category is 0.001gcm according to conductive carrier areal calculation-2~10gcm-2, further excellent
It is selected as 0.01gcm-2~5gcm-2, most preferably 0.05gcm-2~0.2gcm-2, the Na metal phases of certain mass press karat gold category
It is calculated according to certain ratio.
The Na metals are 0.00028gcm according to conductive carrier areal calculation-2~2.8gcm-2, further preferably
0.0028gcm-2~1.4gcm-2, most preferably 0.014gcm-2~0.056gcm-2。
The amount of the K and Na according to a certain percentage, the karat gold belong to quality and Na metals mass ratio be 70~
86：14~30, further preferably 75~81：19~25, it is still more preferably 77~79：21~23.
The karat gold belongs to and Na metals are pure K and pure Na.
The karat gold belongs to and Na metals are using preceding needing cutting removal oxide on surface.
In step 1), karat gold category is heated to 300 DEG C~500 DEG C of temperature, most preferably 350 DEG C~450 DEG C；
By Na METAL HEATING PROCESSs to 300 DEG C~500 DEG C, most preferably 350 DEG C~450 DEG C of temperature.
In step 2), the combination electrode of acquisition can be infiltrated to the selfreparing oxidation obtained in the electrolytic solution containing new component
Film.
The selfreparing oxidation film is mainly wrapped in electrode surface with form membrane.
The electrolyte solute is KPF6、KClO4、KTFSI、NaPF6、NaClO4, NaTFSI etc. it is one or more kinds of mixed
The electrolyte of conjunction；Solvent is that ethylene carbonate (EC), DEC, dimethyl carbonate (DMC), DIGLYM, PC etc. are one or more kinds of mixed
The solution and various additives of conjunction, such as additive containing F etc..Further preferably, solute is molar ratio in the electrolyte
1：1 KPF6And NaPF6, solvents are by volume ratio 1 in the electrolyte：1 ethylene carbonate (EC) and dimethyl carbonate
(DMC) solution formed, KPF6And NaPF6Concentration in the electrolytic solution is 0.5mol/L~3mol/L, further preferably
1mol/L。
The new component is high ionic conductivity KF and NaF.
In step 2), the Na-K alloys can be then adsorbed in conductive carrier completely.
The selfreparing oxidation film is by meeting self-healing after mechanical damage.
The mechanical damage is mainly the removal of film, crack, squeeze cause it is broken etc..
In step 1) and step 2), the content of nitrogen or oxygen in inert gas can be adjusted, heterogeneity is obtained
Selfreparing oxidation film.
The inert gas is argon gas, preferably high-purity argon gas.Full of in inert gas environment, water content is less than
0.1ppm。
The content of the nitrogen or oxygen be 0.1ppm~100ppm, further preferably 0.1ppm~10ppm, most
Preferably 0.1ppm~0.5ppm, wherein nitrogen and oxygen content are individually adjusted, need not be at fixed proportion.
It obtains under the Na-K alloy at normal temperature of Na-K alloys combination electrode inside being liquid, surface film oxide is solid-state, is not present
Dendritic growth situation can be used as K ion battery cathode materials and Na ion battery cathode materials simultaneously.
The selfreparing oxidation film cladding Na-K liquid alloy electrodes include conductive carrier, are deposited on conductive carrier
Na-K liquid alloys and the selfreparing oxidation film formed on surface, the i.e. Na-K including being adsorbed on conductive carrier, conductive carrier
The selfreparing oxidation film of liquid alloy and surface
The selfreparing oxidation film coats Na-K liquid alloys electrode answering as alkali metal secondary battery negative material
With.
The present invention compared with the prior art, has the following advantages that and protrudes effect：
The present invention is for preparing with rock-steady structure without dendrite liquid alloy negative electrode.The present invention has following two
Advantage：Conventional electrode structure is mainly that collector and Na-K liquid alloys are constituted, and Na-K liquid alloys are easy to fall off, and lead to electricity
Pole structural instability, the present invention propose that new electrode structure, wherein Na-K alloys combination electrode include conductive substrates, carried in conduction
The Na-K alloys deposited on body, the selfreparing oxidation film formed on surface, the structure can increase the stable structure of electrode structure
Property, enhance electric conductivity, improves high rate capability and coulombic efficiency；Preparation method is convenient, and customary preparation methods need to be heated at high temperature
There is Na-K liquid alloys certain risk, the present invention to obtain selfreparing at normal temperatures by simple physics stacked system
Oxidation film coats Na-K liquid alloy electrodes.The composite negative pole improves the security performance and cycle performance of alkali metal, contributes to
Promote high-energy density, high stability alkali metal secondary battery development.
The present invention efficient selfreparing oxidation film cladding Na-K liquid alloy electrodes have high coulombic efficiency, without dendritic growth and
The features such as stable structure, can be used as potassium metal negative electrode and sodium metal negative electrode, be matched with the positive electrodes such as sulphur, Prussian blue simultaneously
When, significantly improve the energy density and cyclical stability of full battery.
Description of the drawings
Fig. 1 is Research Thinking figure of the present invention；
Fig. 2 is that carbon cloth load Na-K alloys/oxidation film composite electrode prepares schematic diagram；
Fig. 3 coats the XRD diffraction patterns of Na-K liquid alloy electrode surfaces for selfreparing oxidation film obtained in embodiment 1；
After Fig. 4 is selfreparing oxidation film cladding Na-K liquid alloy electrodes obtained dresses up symmetry electrode in embodiment 1
Curve graph under different multiplying.
Specific implementation mode
With reference to embodiment, the present invention will be described in detail, but the present invention is not limited to this.
Embodiment 1
0.1g karat golds are belonged to and 0.028g Na metals are heated separately to 450 DEG C of meltings in glove box, then will be grown with tweezers
Width is that the carbon cloth (thickness 2mm) of 1cm is contacted with two kinds of molten metals respectively, and after all absorbing, taking-up is cooled to room temperature 25 DEG C.
Load karat gold respectively is belonged to and is stacked with the carbon cloth of Na metals, alloying reactions occur in two kinds of metals of carbon cloth surfaces, and in surface shape
At selfreparing oxidation film, after a period of time reacts, that is, selfreparing oxidation film cladding Na-K liquid alloy electrodes are formed.
XRD diffraction patterns such as Fig. 3 institutes of selfreparing oxidation film obtained cladding Na-K liquid alloy electrode surfaces in embodiment 1
Show.As shown, the electrode prepared does not have the characteristic peak that Na metals and karat gold belong to, show that the Na-K that the alloy to be formed is liquid is closed
Gold.Find faint KO simultaneously2And K2The peak of O shows that Na-K alloy surfaces have solid oxide film to be formed, and main ingredient is KO2
And K2O。
Embodiment 2
It is 0.2ppm, nitrogen content 0.1ppm to adjust oxygen content in glove box.0.2g karat golds are belonged to and 0.056g Na
Metal is heated separately to 400 DEG C of meltings in glove box, then with tweezers by length and width be 1cm carbon cloth (thickness 2mm) respectively with two
Kind molten metal contact, after all absorbing, taking-up is cooled to room temperature 25 DEG C.Load karat gold respectively is belonged into the carbon cloth with Na metals
It stacks, alloying reaction occurs in two kinds of metals of carbon cloth surfaces, and selfreparing oxidation film is formed on surface, a period of time reacts
Afterwards, that is, selfreparing oxidation film cladding Na-K liquid alloy electrodes are formed.
The XRD diffraction patterns for obtaining electrode are similar to Example 1, it is found furthermore that a small amount of KN3Peak.
Embodiment 3
0.2g karat golds are belonged to and 0.056g Na metals are heated separately to 400 DEG C of meltings in glove box, then will be grown with tweezers
Width is that the carbon cloth (thickness 2mm) of 1cm is contacted with two kinds of molten metals respectively, and after all absorbing, taking-up is cooled to room temperature 25 DEG C.
By (solute is molar ratio 1 in the carbon cloth immersion electrolyte of load karat gold category respectively and Na metals：1 KPF6And NaPF6；It is organic molten
Agent is by volume ratio 1：The solution of 1 ethylene carbonate (EC) and dimethyl carbonate (DMC) composition, KPF6And NaPF6In the electrolytic solution
Concentration be 1mol/L), and stack, occur alloying reactions in two kinds of metals of carbon cloth surfaces, and surface formed have it is new
The selfreparing oxidation film of ingredient after a period of time reacts, that is, forms selfreparing oxidation film cladding Na-K liquid alloy electrodes.
The XRD diffraction patterns for obtaining electrode are similar to Example 1, it is found furthermore that the peak of a small amount of KF.
Performance test
N selfreparings oxidation film made of above-described embodiment 1~3 is coated into Na-K liquid alloys electrode as button electricity
Pond to electrode and working electrode, electrolyte is 1M KPF6(or 1M NaPF6) in electrolyte, current density is 1mA cm-2,
Cycle electricity is 1mAh cm-2, in 25 ± 1 DEG C of environment measure symmetry electrode system in K (or Na) metal negative electrode it is excessively electric
Position.
The performance test results are as follows：
The Na-K alloy combination electrodes of embodiment 1, embodiment 2 and embodiment 3 are in 1mAcm-2200 are recycled under current density
Secondary, overvoltage can be stablized within 22mV, 19mV and 17mV respectively, and voltage platform is stablized, and without apparent fluctuation, and not have oxidation film
Na-K liquid alloy combination electrode potential fluctuations it is violent.In addition, the coulombic efficiency that electrode cycle 100 encloses can be respectively maintained at
97.9%, 98.5% and 99.2% or more.As it can be seen that the overvoltage of Na-K alloys combination electrode obtained above is low, stable circulation
Property it is good, coulombic efficiency is high.Selfreparing oxidation film obtained coats Na-K liquid alloy electrode assemblings into symmetry electrode in embodiment 1
The curve graph under different multiplying afterwards is as shown in Figure 4.
This is because the Na-K alloys that exist for of selfreparing oxidation film provide stable interface, and liquid form under room temperature
Existing Na-K alloys avoid the generation of dendrite, ensure that the stability of electrode structure.
Therefore, the efficient selfreparing oxidation film cladding Na-K liquid alloy electrodes of the present invention have high coulombic efficiency, significantly suppression
The features such as dendritic growth processed and interfacial structure are stablized, being modified in the metal negative electrode of alkali metal secondary battery has guidance well
Meaning, this method contribute to the large-scale application of no dendrite alkali metal cathode.
Claims (10)
1. a kind of preparation method of selfreparing oxidation film cladding Na-K liquid alloy electrodes, which is characterized in that include the following steps：
1) under inert gas protection, karat gold is belonged to and being heated, until fusing, then conductive carrier is contacted with the karat gold category of fusing, it melts
The karat gold of change belongs to slowly moistening conductive carrier, and after all absorbing, the conductive carrier that load karat gold belongs to is obtained after cooling；
Under inert gas protection, by Na METAL HEATING PROCESSs, until melting, then conductive carrier is contacted with the Na metals of fusing, is melted
The Na metals of change slowly moisten conductive carrier, and after all absorbing, the conductive carrier of load Na metals is obtained after cooling；
2) under inert gas protection, the conductive carrier that load karat gold prepared by step 1) belongs to is carried with the conductive of load Na metals
Body physics stacks, and karat gold category and the metallic alloying reactions of Na occurs, and generate oxidation film simultaneously, obtains selfreparing oxidation film cladding
Na-K liquid alloy electrodes；
Alternatively, infiltrating the conductive carrier of conductive carrier and load Na metals that load karat gold prepared by step 1) belongs in electrolyte
In, and stack, alloying reaction occurs, and generate selfreparing oxidation film simultaneously, obtains selfreparing oxidation film and coat Na-K liquid
Alloy electrode.
2. preparation method according to claim 1, which is characterized in that in step 1), karat gold category is heated to 300 DEG C of temperature
~500 DEG C；
By Na METAL HEATING PROCESSs to 300 DEG C~500 DEG C of temperature.
3. preparation method according to claim 1, which is characterized in that in step 1), the conductive carrier is carbon cloth.
4. preparation method according to claim 1, which is characterized in that in step 1), the thickness of the conductive carrier is
0.5mm~5mm；
The area of the conductive carrier is 0.2cm2~2cm2。
5. preparation method according to claim 1, which is characterized in that in step 1), the karat gold category is according to conductive carrier
Areal calculation is 0.01gcm-2~5gcm-2；
The Na metals are 0.0028gcm according to conductive carrier areal calculation-2~1.4gcm-2。
6. preparation method according to claim 1, which is characterized in that in step 1), the quality and Na that the karat gold belongs to are golden
The mass ratio of category is 70~86：14~30.
7. preparation method according to claim 1, which is characterized in that in step 2), solute is to rub in the electrolyte
That ratio 1：1 KPF6And NaPF6, solvents are by volume ratio 1 in the electrolyte：1 ethylene carbonate and dimethyl carbonate
The solution of composition, KPF6And NaPF6Concentration in the electrolytic solution is 0.5mol/L~3mol/L.
8. coating Na-K liquid alloys according to selfreparing oxidation film prepared by claim 1~7 any one of them preparation method
Electrode.
9. selfreparing oxidation film according to claim 8 coats Na-K liquid alloy electrodes, which is characterized in that including conduction
Carrier, the Na-K liquid alloys deposited on conductive carrier and the selfreparing oxidation film formed on surface.
10. selfreparing oxidation film according to claim 8 coats Na-K liquid alloy electrodes as alkali metal secondary battery
The application of negative material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810140846.3A CN108400316B (en) | 2018-02-11 | 2018-02-11 | Self-repairing oxide film coated Na-K liquid alloy electrode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810140846.3A CN108400316B (en) | 2018-02-11 | 2018-02-11 | Self-repairing oxide film coated Na-K liquid alloy electrode and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108400316A true CN108400316A (en) | 2018-08-14 |
| CN108400316B CN108400316B (en) | 2020-08-18 |
Family
ID=63095276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810140846.3A Active CN108400316B (en) | 2018-02-11 | 2018-02-11 | Self-repairing oxide film coated Na-K liquid alloy electrode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108400316B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109244441A (en) * | 2018-08-29 | 2019-01-18 | 浙江大学 | Non-newtonian flow posture Na-K alloy electrode and its preparation method and application |
| CN109244323A (en) * | 2018-09-17 | 2019-01-18 | 浙江大学 | A kind of preparation method and application of low cost alkali metal battery diaphragm |
| CN109273672A (en) * | 2018-08-29 | 2019-01-25 | 浙江大学 | SEI film cladding Na-K liquid alloy electrode in situ and its preparation method and application |
| CN110649227A (en) * | 2019-09-18 | 2020-01-03 | 天津大学 | Three-dimensional composite potassium metal cathode and preparation method and application thereof |
| CN113113593A (en) * | 2021-02-26 | 2021-07-13 | 华北理工大学 | Room temperature solid sodium ion battery based on liquid alloy |
| CN113258035A (en) * | 2021-05-12 | 2021-08-13 | 哈尔滨工业大学 | Dendrite-free alloy cathode with solid-liquid phase conversion mechanism and preparation method thereof |
| CN113745464A (en) * | 2021-07-13 | 2021-12-03 | 南京工业大学 | Preparation and application of liquid sodium-potassium alloy @ flexible hollow carbon paper electrode |
| CN114094042A (en) * | 2021-11-10 | 2022-02-25 | 惠州亿纬锂能股份有限公司 | Liquid metal negative pole piece and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595683A (en) * | 2003-09-10 | 2005-03-16 | 中国科学院物理研究所 | Nanometer metal or alloy composite material and preparation and usage thereof |
| CN1909265A (en) * | 2006-07-13 | 2007-02-07 | 昆明理工大学 | Lithium ion battery negative electrode prepared by metal nano-wire and its preparation method |
| CN104716330A (en) * | 2015-03-25 | 2015-06-17 | 中国科学院化学研究所 | Three-dimensional porous current collector as well as preparation method and use thereof |
| CN106571458A (en) * | 2016-11-14 | 2017-04-19 | 苏州赛福德备贸易有限公司 | Anode composite material, and preparation method thereof |
-
2018
- 2018-02-11 CN CN201810140846.3A patent/CN108400316B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1595683A (en) * | 2003-09-10 | 2005-03-16 | 中国科学院物理研究所 | Nanometer metal or alloy composite material and preparation and usage thereof |
| CN1909265A (en) * | 2006-07-13 | 2007-02-07 | 昆明理工大学 | Lithium ion battery negative electrode prepared by metal nano-wire and its preparation method |
| CN104716330A (en) * | 2015-03-25 | 2015-06-17 | 中国科学院化学研究所 | Three-dimensional porous current collector as well as preparation method and use thereof |
| CN106571458A (en) * | 2016-11-14 | 2017-04-19 | 苏州赛福德备贸易有限公司 | Anode composite material, and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109244441A (en) * | 2018-08-29 | 2019-01-18 | 浙江大学 | Non-newtonian flow posture Na-K alloy electrode and its preparation method and application |
| CN109273672A (en) * | 2018-08-29 | 2019-01-25 | 浙江大学 | SEI film cladding Na-K liquid alloy electrode in situ and its preparation method and application |
| CN109244441B (en) * | 2018-08-29 | 2020-06-05 | 浙江大学 | non-Newtonian fluid Na-K alloy electrode and preparation method and application thereof |
| CN109244323A (en) * | 2018-09-17 | 2019-01-18 | 浙江大学 | A kind of preparation method and application of low cost alkali metal battery diaphragm |
| CN109244323B (en) * | 2018-09-17 | 2020-08-18 | 浙江大学 | Preparation method and application of low-cost alkali metal battery diaphragm |
| CN110649227A (en) * | 2019-09-18 | 2020-01-03 | 天津大学 | Three-dimensional composite potassium metal cathode and preparation method and application thereof |
| CN113113593A (en) * | 2021-02-26 | 2021-07-13 | 华北理工大学 | Room temperature solid sodium ion battery based on liquid alloy |
| CN113258035A (en) * | 2021-05-12 | 2021-08-13 | 哈尔滨工业大学 | Dendrite-free alloy cathode with solid-liquid phase conversion mechanism and preparation method thereof |
| CN113258035B (en) * | 2021-05-12 | 2022-05-17 | 哈尔滨工业大学 | Dendrite-free alloy cathode with solid-liquid phase conversion mechanism and preparation method thereof |
| CN113745464A (en) * | 2021-07-13 | 2021-12-03 | 南京工业大学 | Preparation and application of liquid sodium-potassium alloy @ flexible hollow carbon paper electrode |
| CN113745464B (en) * | 2021-07-13 | 2022-09-27 | 南京工业大学 | Preparation and application of liquid sodium-potassium alloy @ flexible hollow carbon paper electrode |
| CN114094042A (en) * | 2021-11-10 | 2022-02-25 | 惠州亿纬锂能股份有限公司 | Liquid metal negative pole piece and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108400316B (en) | 2020-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108400316A (en) | Selfreparing oxidation film coats Na-K liquid alloy electrodes and its preparation method and application | |
| Chu et al. | Recent advanced skeletons in sodium metal anodes | |
| CN110061191B (en) | Three-dimensional metal lithium cathode and preparation method and application thereof | |
| CN113629236B (en) | Composite metal lithium cathode and preparation method and application thereof | |
| CN111900333B (en) | Lithium-free dendritic crystal anode with carbon nanotube film directly compounded with molten lithium metal and preparation method thereof | |
| CN111106310A (en) | Preparation method of composite lithium metal negative electrode and battery containing composite lithium metal negative electrode | |
| CN108899580A (en) | A kind of lithium ion solid conductor, preparation method and solid lithium battery | |
| CN104701588A (en) | High-compactness solid electrolyte-based novel lithium air battery | |
| CN110071284A (en) | The guard method of metal lithium electrode | |
| CN105810924B (en) | A kind of carbon coating alloy material and its preparation method and application | |
| CN109273672B (en) | Na-K liquid alloy electrode coated with in-situ SEI film as well as preparation method and application thereof | |
| CN108183197A (en) | A kind of composite metal lithium negative pole structure and preparation method thereof | |
| CN109950547A (en) | A kind of three-dimensional collector being modified with base metal coating | |
| CN108063219A (en) | A kind of high efficiency liquid alkali metal alloy electrode and its preparation method and application | |
| CN112928238B (en) | Ultrathin metal lithium electrode, preparation thereof and application of ultrathin metal lithium electrode as negative electrode of secondary lithium battery | |
| Wang et al. | Fabrication and electrochemical properties of the Sn–Ni–P alloy rods array electrode for lithium-ion batteries | |
| CN108199014A (en) | A kind of porous nitrogen-doped carbon/Fe2O3/ grapheme foam flexible composite, preparation method and applications | |
| CN115832217A (en) | Metal lithium composite negative electrode for secondary battery and preparation method thereof | |
| Yuan et al. | Dendrite-free NaK alloy Anodes: Electrodes preparation and interfacial reaction | |
| Zhang et al. | Stable Li/Cu2O composite anodes enabled by a 3D conductive skeleton with lithiophilic nanowire arrays | |
| Jiang et al. | Long-life and efficient sodium metal anodes enabled by a sodiophilic matrix | |
| CN113948676A (en) | Alkali metal cathode protected by boron-oxygen-based interface film, preparation method and application | |
| Hou et al. | Dendrite-free and stable Zn metal anodes with ZnO protective layer | |
| CN109037627A (en) | A kind of alkali metal base composite negative pole and its application | |
| CN113488656A (en) | 3D lithium-philic composite porous metal alloy current collector 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |