CN109671902A - A kind of long-life lithium metal battery cathode preparation method and lithium battery - Google Patents
A kind of long-life lithium metal battery cathode preparation method and lithium battery Download PDFInfo
- Publication number
- CN109671902A CN109671902A CN201811436510.8A CN201811436510A CN109671902A CN 109671902 A CN109671902 A CN 109671902A CN 201811436510 A CN201811436510 A CN 201811436510A CN 109671902 A CN109671902 A CN 109671902A
- Authority
- CN
- China
- Prior art keywords
- lithium
- metal
- battery
- long
- electrolyte
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si 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
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of long-life lithium metal battery cathode preparation method and lithium metal battery；The present invention is using lithium metal as cathode, it is to electrode with dissimilar metal, ion containing dissimilar metal in electrolyte is assembled into a button cell, and charge certain time under low current, to form one layer of dissimilar metal film in lithium anode surface in situ, the dissimilar metal film can effectively inhibit the growth of Li dendrite with stable metal lithium/electrolyte interface, reduce battery polarization, the Disposal degree of lithium anode is improved, and then improves the performance of lithium metal battery.The method is simple and easy, has broad application prospects.
Description
Technical field
The invention belongs to field of chemical power source, also belong to technical field of energy material.More particularly to long-life lithium metal electricity
Pond cathode preparation method and long-life lithium metal battery cathode preparation method and lithium battery.
Background technique
Lithium metal has high theoretical specific capacity and extremely low electrochemical potentials, and lithium metal battery is answered as the world today
With widest and most promising one of battery, it is considered by the lithium-air battery of cathode and lithium-sulfur cell of lithium metal
It is the next-generation energy-storage battery got a good chance of.However, there are still various problems to need to solve for the practical application of lithium an- ode
Certainly, most important of which is that solve the lithium of metallic lithium surface in battery charge and discharge process since non-uniform deposition/dissolution is made
At Li dendrite formation and growth.
Currently, commonly the method for Li dendrite is inhibited mainly to have: being formed in situ by electrolysis additive or other methods
Metallic lithium surface protective layer, the afflux for preparing protective layer by ex situ method, improving collector preparation three-dimensional or other forms
Body, these methods respectively solve the growth question of lithium an- ode dendrite during charge and discharge cycles to a certain extent,
But certain limiting factor is individually present.Latest Progress shows can have from the angle of building lithium composite negative pole
Effect improves the stability in lithium metal morning charge and discharge cycles.Reasonable design can change lithium metal deposition preference, fundamentally
The problem of improving lithium dendrite growth.However for most materials, the combination between lithium metal is weak, that is, has and dredge lithium
Property.Therefore, a kind of suitable complex method is invented to be of great significance to the application of lithium metal battery cathode.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of long-life lithium metal battery cathode preparation method and lithium battery；
There is the heterogeneous of protective effect the purpose of the present invention is the method by electrochemical deposition is formed in situ one layer in metallic lithium surface
Metallic film, dendrite and dead lithium for solving the problems, such as to be formed in lithium metal battery charging process have high operation can
By property.
Lithium metal battery cathode preparation method provided by the invention, metal lithium sheet are used as cathode, dissimilar metal to electricity
Pole contains dissimilar metal salt in electrolyte；It is assembled into button cell by metal lithium sheet, to electrode and electrolyte, with low current perseverance
Constant-current charge certain time makes metal lithium sheet surface in situ generate one layer of dissimilar metal layer, the thickness of the dissimilar metal layer
It is controlled by the size and conduction time of current density；The button cell is dismantled, the metal lithium sheet after modification is lithium
Battery cathode.
Containing in the electrolyte can contain in the metal ion and solvent of metallic lithium surface stably depositing, the electrolyte
Copper, nickel, cobalt, manganese, magnesium, iron, zinc, gold, the salt or their mixture of silver or platinum, solvent is that can dissolve the organic molten of solute
Agent；The concentration of the electrolyte metal ion is 0.001mol/L-1.0mol/L.
Current density is 0.01-2mAh/cm2, charging time 0-24h.The preferred 0.25mAh/cm of current density2, institute
State charging time preferred 2h.
The present invention also provides a kind of lithium battery, the cathode prepared using above-mentioned lithium metal battery cathode preparation method.
Significant technical effect of the invention: it the present invention provides a kind of long-life lithium metal battery cathode preparation method and adopts
With the lithium battery of cathode prepared by the preparation method, lithium metal electricity can be applied to by the lithium metal of dissimilar metal modifying interface
Pond.The present invention is to electrode with dissimilar metal, ion containing dissimilar metal in electrolyte is assembled into one using lithium metal as cathode
A button cell, charge certain time under low current, so that it is thin to form one layer of dissimilar metal in lithium anode surface in situ
Film, the dissimilar metal film can effectively inhibit the growth of Li dendrite with stable metal lithium/electrolyte interface, reduce battery polarization,
The Disposal degree of lithium anode is improved, and then improves the performance of lithium metal battery.The stable metal cathode of lithium prepare it is simple and easy,
It is practical, the lithium anode being prepared have excellent cycle performance, can be used as the long-life, high-specific energy battery into
Row application, has great market potential and prospect, and this method has great industrial application value.
Detailed description of the invention
Fig. 1 m- voltage curve when being lithium-lithium Symmetrical cells of the embodiment 1 by modification front and back.
Fig. 2 is lithium-lithium titanate battery specific capacity-voltage curve of the modification of embodiment 1 front and back.
Specific embodiment
The present invention is further explained in the light of specific embodiments.Test method described in following embodiments, if nothing
Specified otherwise, the kit material obtain from commercial channels.
Lithium battery of the invention, by long-life lithium metal battery cathode preparation method preparation cathode, battery case anode, just
Pole pole piece, lithium ion electrical conductance electrolyte, diaphragm, cathode pole piece, battery case cathode are assembled into battery, the work of the lithium battery
Temperature is 30 DEG C~50 DEG C of ﹣.
The lithium ion electrical conductance electrolyte mainly includes but is limited to now to be applied to all kinds of lithium-ion battery electrolytes, such as
1.2M LiPF6/ EC:EMC 3:7 (v:v) or 1.0M LiTFSI/DME:DOL 1:1 (v:v).
The diaphragm is existing commercial all kinds of diaphragms, preferably Celgard 2325.
The material of the anode pole piece mainly includes but is not limited to show all kinds of lithium ion batteries sold and applied in market
Or lithium metal battery material, such as LiFePO4, sulphur carbon material or lithium titanate material.
The preparation method comprises the following steps: metal lithium sheet is as cathode, dissimilar metal is used as to electrode, electricity long-life lithium metal battery cathode
It solves and contains dissimilar metal salt in liquid；It is assembled into button cell by metal lithium sheet, to electrode and electrolyte, with low current constant current
Charge certain time, and metal lithium sheet surface in situ is made to generate one layer of dissimilar metal layer, and the thickness of the dissimilar metal layer passes through electricity
The size of current density and conduction time control；The button cell is dismantled, the metal lithium sheet after modification is that lithium battery is negative
Pole.
Embodiment 1.
1. pre-processing the preparation of electrolyte.
In glove box, will be bis- (trifluoromethane sulfonic acid) imines magnesium and magnesium chloride be dissolved in organic solvent tetrahydrofuran,
It is configured to pretreatment electrolyte: 0.25M MgTFSI/0.5MgCl2/THF。
2. the deposition of dissimilar metal magnesium.
Using lithium metal as cathode, magnesium sheet is used as to electrode, and above-mentioned pretreatment electrolyte is assembled into button as electrolyte
Battery, with constant current 0.25mA/cm2Charge 2h, takes out sheet metal after charging in glove box, is washed with dimethyl carbonate
It washs 3 times, removes the remaining electrolyte of adsorption, the lithium metal after obtaining the modification of dissimilar metal magnesium.
3. assembling lithium-lithium Symmetrical cells.
The metal lithium sheet after metal lithium sheet, diaphragm, modification after being sequentially placed into modification in CR2016 type button cell shell,
Suitable electrolyte 1.0M LiTFSI/DME:DOL 1:1 (v:v) is added, is compacted, lithium metal-lithium battery after being modified.
5. lithium metal-lithium Symmetrical cells electro-chemical test.
With constant current 0.5mA/cm on charging/discharging apparatus2Charge and discharge, each charge and discharge process continue 1h, as shown in Figure 1,
Its voltage polarizing is lower than ± 10mV, and charging/discharging voltage platform is symmetrical, and after recycling 500h, voltage curve is still stable, shows to repair
Lithium an- ode after decorations is provided with stable interface, and the generation of Li dendrite is effectively suppressed, and presents good cycle performance.
In contrast, experiment proves that unmodified lithium-lithium Symmetrical cells under identical condition, voltage polarizing ± 70mV a left side
The right side, with the progress of charge and discharge, the polarization of battery is more than 100mV, illustrates that the metal lithium electrode and electrolyte without protection continue
Reaction, produces the SEI film of high impedance, and after the charge and discharge time reaching 400h, voltage acute variation shows that the internal resistance of cell increases
Greatly.
6. assembling lithium-lithium titanate battery.
Metal lithium sheet, diaphragm, metatitanic acid pole piece after being sequentially placed into modification in CR2016 type button cell shell are added suitable
The electrolyte 1.2M LiPF of amount6/ EC:EMC 3:7 (v:v), compacting, lithium metal-lithium titanate battery after being modified.
7. lithium metal-lithium titanate battery electro-chemical test.
Carry out constant current charge-discharge test, work under 2C multiplying power by lithium titanate quality in pole piece in charge and discharge electrical measurement equipment
1-2.5V is set as voltage range.As shown in Fig. 2, lithium metal-lithium titanate battery polarization after modification is smaller, circulation is after 1000 weeks
It is the 86.7% of initial capacity still with the specific capacity of 138.2mAh/g, and unmodified lithium metal-lithium titanate battery is same
After recycling 1000 weeks under the conditions of sample, specific capacity 83.5mAh/g is the 52.4% of initial capacity, the lithium battery after showing modification
Show superior reversible capacity and cyclical stability.
In conclusion one layer of heterogeneous gold is formed in situ in metallic lithium surface in the method that simple low current deposits in the present invention
Belong to film, according to lithium-lithium Symmetrical cells and lithium-lithium titanate full battery charge-discharge test, shows that the invention improves Li dendrite
Growth question, improve the cyclical stability of lithium metal battery, operation is simple, and cost is relatively low, presents wide answer
Use prospect.
Embodiment 2.
The lithium an- ode current density for preparing modification is different, is 0.1mAh/cm2, remaining is same as Example 1.
Embodiment 3.
In glove box, will be bis- (trifluoromethane sulfonic acid) imines magnesium and magnesium chloride be dissolved in organic solvent glycol dimethyl ether
In, it is configured to pretreatment electrolyte: 0.25M MgTFSI/0.5MgCl2/DME.According to the side of 1 small current electro-deposition of embodiment
Method, the metal lithium electrode after preparing modification, is assembled into lithium-lithium Symmetrical cells and lithium-lithium titanate battery.
Claims (6)
1. a kind of long-life lithium metal battery cathode preparation method, which is characterized in that metal lithium sheet is made as cathode, dissimilar metal
To contain dissimilar metal salt in electrolyte to electrode；It is assembled into button cell by metal lithium sheet, to electrode and electrolyte, with small
Electric current constant current charging certain time makes metal lithium sheet surface in situ generate one layer of dissimilar metal layer, the dissimilar metal layer
Thickness controlled by the size and conduction time of current density；The button cell is dismantled, the metal lithium sheet after modification
As cathode of lithium battery.
2. long-life lithium metal battery cathode preparation method as described in claim 1, which is characterized in that contain in the electrolyte
Having can be in the metal ion and solvent of metallic lithium surface stably depositing.
3. long-life lithium metal battery cathode preparation method as claimed in claim 2, which is characterized in that the electrolyte contains
Copper, nickel, cobalt, manganese, magnesium, iron, zinc, gold, the salt or their mixture of silver or platinum, solvent are the organic solvent that can dissolve solute；
The concentration of the electrolyte metal ion is 0.001mol/L-1.0mol/L.
4. long-life lithium metal battery cathode preparation method as described in claim 1, which is characterized in that current density is
0.01-2mAh/cm2, charging time 0-24h.
5. long-life lithium metal battery cathode preparation method as described in claim 1, which is characterized in that current density is
0.25mAh/cm2, charging time 2h.
6. a kind of lithium battery, which is characterized in that including long-life lithium metal electricity described in any claim in claim 1-4
The cathode of pond cathode preparation method preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811436510.8A CN109671902A (en) | 2018-11-28 | 2018-11-28 | A kind of long-life lithium metal battery cathode preparation method and lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811436510.8A CN109671902A (en) | 2018-11-28 | 2018-11-28 | A kind of long-life lithium metal battery cathode preparation method and lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109671902A true CN109671902A (en) | 2019-04-23 |
Family
ID=66143309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811436510.8A Pending CN109671902A (en) | 2018-11-28 | 2018-11-28 | A kind of long-life lithium metal battery cathode preparation method and lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109671902A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110783551A (en) * | 2019-11-13 | 2020-02-11 | 华南师范大学 | Lithium electrode material, preparation method thereof and battery containing lithium electrode material |
| CN112490411A (en) * | 2020-11-25 | 2021-03-12 | 哈尔滨工业大学 | Method for protecting lithium metal negative electrode through in-situ film forming |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06140026A (en) * | 1992-10-20 | 1994-05-20 | Mitsubishi Cable Ind Ltd | Lithium secondary battery |
| 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 |
| CN105845894A (en) * | 2016-05-04 | 2016-08-10 | 合肥国轩高科动力能源有限公司 | Method and device for pre-lithiation of lithium ion battery negative pole piece |
| CN108063218A (en) * | 2017-12-19 | 2018-05-22 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of preparation method of sheet metal lithium base cathode |
-
2018
- 2018-11-28 CN CN201811436510.8A patent/CN109671902A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06140026A (en) * | 1992-10-20 | 1994-05-20 | Mitsubishi Cable Ind Ltd | Lithium secondary battery |
| 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 |
| CN105845894A (en) * | 2016-05-04 | 2016-08-10 | 合肥国轩高科动力能源有限公司 | Method and device for pre-lithiation of lithium ion battery negative pole piece |
| CN108063218A (en) * | 2017-12-19 | 2018-05-22 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of preparation method of sheet metal lithium base cathode |
Non-Patent Citations (1)
| Title |
|---|
| FULU CHU ET AL.: "In Situ Plating of Porous Mg Network Layer to Reinforce Anode Dendrite Suppression in Li-Metal Batteries", 《ACS APPLIED MATERIALS & INTERFACES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110783551A (en) * | 2019-11-13 | 2020-02-11 | 华南师范大学 | Lithium electrode material, preparation method thereof and battery containing lithium electrode material |
| CN112490411A (en) * | 2020-11-25 | 2021-03-12 | 哈尔滨工业大学 | Method for protecting lithium metal negative electrode through in-situ film forming |
| CN112490411B (en) * | 2020-11-25 | 2022-04-12 | 哈尔滨工业大学 | Method for protecting lithium metal negative electrode through in-situ film forming |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102651485B (en) | The application in rechargeable magnesium cell of rechargeable magnesium cell, electrolyte and the electrolyte for rechargeable magnesium cell | |
| CN105789690B (en) | Rechargeable magnesium battery and preparation method thereof | |
| US20210296641A1 (en) | Supporter of lithium metal and methods thereof | |
| CN108039514B (en) | Electroplating preparation method of lithium ion battery with reference electrode | |
| CN106229498A (en) | A kind of negative material being applicable to Water based metal ion battery and preparation method thereof | |
| CN106133979A (en) | Extended-life lithium ion battery | |
| CN102903973A (en) | Battery | |
| CN109830646A (en) | A kind of composite metal negative pole and the battery comprising the cathode | |
| CN102903924A (en) | Battery | |
| CN103094627A (en) | Battery | |
| CN101752554B (en) | Method for preparing Sn-Zn alloy cathode material of lithium ion battery | |
| CN109037594A (en) | A kind of alkali metal cathode and the preparation method and application thereof that self-healing is polymer-modified | |
| Li et al. | The effects of lithium salt and solvent on lithium metal anode performance | |
| CN108493485A (en) | A kind of preparation method of high power capacity high safety solid state lithium battery | |
| CN103094583A (en) | Battery and treatment method of battery current collector | |
| CN112234195A (en) | Chargeable and dischargeable water system zinc ion full cell | |
| CN109286013A (en) | A kind of lithium ion battery high pressure lithium-rich manganese-based anode material and its coating modification methods and applications coating polyamide organic matter layer | |
| CN112670574A (en) | Electrolyte for metal battery and metal battery | |
| CN113363427A (en) | Preparation method of lithium alloy cathode for sulfide all-solid-state battery and battery thereof | |
| CN103474698B (en) | The chargeable lithium battery electrolyte of the high dissolution efficiency of lithium metal high deposition and preparation thereof | |
| CN109671902A (en) | A kind of long-life lithium metal battery cathode preparation method and lithium battery | |
| CN112736239B (en) | Zinc ion battery cathode, preparation method thereof and zinc ion battery | |
| CN110350146B (en) | Modified three-dimensional porous antimony electrode, preparation method and application | |
| CN116914119A (en) | Lithium supplementing anode and preparation method and application thereof | |
| CN102163712B (en) | Preparation method of sulfur positive material of lithium sulfur battery |
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: 20190423 |