CN204885286U - Lithium metal negative pole of high security - Google Patents
Lithium metal negative pole of high security Download PDFInfo
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- CN204885286U CN204885286U CN201520484709.3U CN201520484709U CN204885286U CN 204885286 U CN204885286 U CN 204885286U CN 201520484709 U CN201520484709 U CN 201520484709U CN 204885286 U CN204885286 U CN 204885286U
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- lithium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The utility model provides a lithium metal negative pole of high security, including lithium powder porous electrode and silica -based protective layer, silica -based protective layer coating by vaporization is in on the lithium powder porous electrode, the thickness of silica -based protective layer is 0.02-0.2 mu m. Adopt the technical scheme of the utility model, the coating by vaporization one deck has and stores up the silica -based protection film of lithium function on lithium metal powder electrode, and the security that has improved the lithium metal negative pole greatly has than high current density, and the internal resistance is less, has improved the cycle efficiency simultaneously, provides development space for the application of lithium metal negative pole in the high energy battery field.
Description
Technical field
The utility model belongs to technical field of lithium batteries, relates to a kind of lithium anode, particularly relates to a kind of lithium anode of high security.
Background technology
Lithium ion battery has the advantages such as energy storage is large, pollution-free, lightweight, is used widely in the field such as portable electric appts, electric tool.But also there are some development bottlenecks in the large-sized battery such as electric automobile, energy storage application: safety in utilization, cycle life, energy density etc.
Lithium ion battery take graphite as negative pole, and graphite negative electrodes theoretical capacity is 375mAh/g, can not meet the demand of energy-density lithium ion battery.Compared to graphite negative electrodes, lithium anode highlights numerous advantage, higher specific energy, the theoretical capacity of lithium metal is up to 3861mAh/g, but because lithium anode easily produces dendrite in charge and discharge process, not only make cycle performance decline, time serious, also can cause internal short-circuit, security incident occurs.So suppress the growth of Li dendrite, improving cycle efficieny, is the key developing with lithium the high-energy-density secondary cell being negative pole.
For suppressing lithium anode to generate Li dendrite in charge and discharge cycles, researcher has done large quantity research, mainly concentrates in the surface modification work of anticathode lithium, existing many surface propertys by using electrolysis additive to carry out modification cathode of lithium; But this monistic modified effect can't reach practical standard, and easily cause the drawbacks such as capacitance loss, internal resistance increase, chemical property variation.
Utility model content
For above-mentioned technical problem, the utility model provides a kind of lithium anode of high security, substantially increase the fail safe of lithium anode, there is higher current density, internal resistance is less, improve cycle efficieny, for lithium anode provides development space in the application in high energy battery field simultaneously.
To this; the technical solution adopted in the utility model is: a kind of lithium anode of high security; comprise lithium powder porous electrode and silica-based protective layer, described silica-based protective layer evaporation is on described lithium powder porous electrode, and the thickness of described silica-based protective layer is 0.02 ~ 0.2 μm.Wherein, described silica-based protective layer is adopted by silica-base material the mode evaporation of vacuum coating to be formed on described lithium powder porous electrode.
In such scheme; because lithium powder porous electrode is powder porous electrode; described silica-based protective layer adopt vacuum coating mode by silica-base material evaporation described lithium powder porous electrode lithium powder on the surface time; described silica-base material can enter into lithium metal powder porous between gap; thus penetrate in lithium powder porous electrode; thus can better protect lithium anode, prevent it from charge and discharge process, forming Li dendrite, also better compensate for the capacitance loss of plated film negative pole.
Described silica-based protective layer has certain storage lithium effect; and with lithium metal powder electrode based on; lithium metal in the lithium metal powder electrode be directly connected with collector; make the silica-base material in described silica-based protective layer be in shallow charging and discharging state always; described silica-based protective layer in charge and discharge process compared with independent silicon-based anode; its change in volume is less, is conducive to the safeguard protection effect of the stable performance of silica-based protective layer to lithium metal, does not affect the performance of lithium anode simultaneously.
Adopt this technical scheme, the evaporation silica-based protective layer of one deck on lithium metal powder electrode, described silica-based protective layer has storage lithium function, not only serves protective effect and prevents from forming Li dendrite, also compensate for the capacitance loss of plated film negative pole; In addition; lithium powder electrode has larger specific area; the silica-based protective layer of evaporation one deck is adopted to enhance conjugation; make diaphragm and substrate contact more intact; like this for lithium metal powder electrode provides larger current density and less internal resistance; while the energy improving battery, also improve battery rate charge-discharge ability and useful life.
As further improvement of the utility model, the thickness of described silica-based protective layer is 0.04 ~ 0.1 μm.
As further improvement of the utility model, described lithium powder porous electrode comprises lithium powder and collector, and described lithium powder porous electrode is coated on collector, by what formed after compressing tablet after lithium powder and binding agent being mixed in a solvent; Wherein, described solvent is oxolane.
As further improvement of the utility model, the particle diameter of described lithium powder is 10 ~ 100 μm.
As further improvement of the utility model, the particle diameter of described lithium powder is 18 ~ 30 μm.
As further improvement of the utility model, described collector is Copper Foil.
Further, the lithium anode of described a kind of high security adopts following steps to prepare:
Step S1: after the lithium metal of melting is mixed with hot silicone oil, stir, the temperature of described hot silicone oil is 230 ~ 250 DEG C, and mixing speed is 25000 ~ 30000rpm; Then be cooled to room temperature, obtain metallic lithium powder, after cyclohexane washing, it is 18 ~ 30 μm of metallic lithium powders that drying obtains particle size distribution.
Step S2: described metallic lithium powder is mixed with binding agent PVDF, then oxolane is added, in de-airing mixer, stir 1 ~ 6h mix slurry, then described slurry is applied on the Copper Foil of anticipating, carries out drying, compressing tablet obtains lithium powder porous electrode; Described anticipate refer to Copper Foil is cleaned, the conventional treatment such as dedusting.
Step S3: vacuum chamber silica-base material and described lithium powder porous electrode being put into vacuum coating equipment; under vacuum; silica-base material is evaporated; it is 0.04 ~ 0.1 μm of silica-based protective layer that gas ionization atomic deposition forms thickness on the surface of described lithium powder porous electrode, obtains the lithium anode of high security.
Further optimization, in step S1, the temperature of described hot silicone oil is 240 DEG C, and described mixing speed is 28000rpm.
Further optimization, the mass ratio of described metallic lithium powder and binding agent PVDF is 90:10 ~ 80:20; Further optimization, 1.5 ~ 2.0 times that the quality of described oxolane is described metallic lithium powder and binding agent PVDF gross mass.
Further optimization, in step S2, the described time of stirring in de-airing mixer is 2 ~ 4h.
Further optimization, in step S2, the vacuum pressure of described vacuum condition is 10
-4~ 10
-2pa.
Further optimization, described silica-base material is at least one in amorphous silicon or siloxanes.
For the preparation method of the lithium anode of above-mentioned high security, comprise the following steps:
Step S1: after the lithium metal of melting is mixed with hot silicone oil, stir, the temperature of described hot silicone oil is 230 ~ 250 DEG C, and mixing speed is 25000 ~ 30000rpm; Then be cooled to room temperature, obtain metallic lithium powder, after cyclohexane washing, it is 18 ~ 30 μm of metallic lithium powders that drying obtains particle size distribution.
Step S2: described metallic lithium powder is mixed with binding agent PVDF, then oxolane is added, in de-airing mixer, stir 1 ~ 6h mix slurry, then described slurry is applied on the Copper Foil of anticipating, carries out drying, compressing tablet obtains lithium powder porous electrode.
Step S3: vacuum chamber silica-base material and described lithium powder porous electrode being put into vacuum coating equipment, 10
-4~ 10
-2under the vacuum condition of Pa, evaporated by silica-base material, it is 0.04 ~ 0.1 μm of silica-based protective layer that gas ionization atomic deposition forms thickness on the surface of described lithium powder porous electrode, obtains the lithium anode of high security; Wherein, described silica-base material is at least one in amorphous silicon or siloxanes.
Compared with prior art, the beneficial effects of the utility model are:
First; the lithium anode of described high security is the evaporation silica-based diaphragm of one deck on lithium powder electrode; described silica-based diaphragm has storage lithium function; not only serve protective effect; prevent it from charge and discharge process, forming Li dendrite; also compensate for the capacitance loss of plated film negative pole, obtained serondary lithium battery has higher capacity.
Second; lithium powder electrode has larger specific area; the silica-based diaphragm of evaporation one deck is adopted to enhance conjugation; diaphragm is made to contact more intact with the lithium powder layer of lithium powder porous electrode; like this for lithium metal powder electrode provides larger current density and less internal resistance; while the energy improving battery, also improve battery rate charge-discharge ability and useful life.
3rd, the lithium anode superior performance of the technical program, use safety, and simple for production, can be used for actual production.
The serondary lithium battery adopting the high security lithium anode of the technical solution of the utility model to prepare obviously improves compared to the conventional batteries performance of same size: battery capacity is up to 1583mAh/g, and first charge-discharge coulombic efficiency is more than 90%; Reduce the internal resistance of cell, improve high-rate battery discharge performance, capability retention during 10C multiplying power discharging is up to more than 90% during 1C multiplying power discharging; Improve useful life, after 500 circulations, reversible capacity conservation rate is up to more than 70%.
Accompanying drawing explanation
Fig. 1 is the STRUCTURE DECOMPOSITION schematic diagram of a kind of embodiment of the utility model.
Fig. 2 is a kind of embodiment schematic cross-section of the utility model.
Mark in figure: 1-silica-based protective layer; 2-lithium powder porous electrode; 21-lithium powder material layer; 22-Copper Foil.
Embodiment
Below in conjunction with accompanying drawing, preferably embodiment of the present utility model is described in further detail.
Embodiment 1
As depicted in figs. 1 and 2, a kind of lithium anode of high security, comprises lithium powder porous electrode 2 and silica-based protective layer 1, also comprises negative lug; Described lithium powder porous electrode 2 comprises lithium powder material layer 21 and Copper Foil 22, and described lithium powder porous electrode 2 is coated on Copper Foil 22, by what formed after compressing tablet after lithium powder and binding agent PVDF being mixed in tetrahydrofuran solvent; Described silica-based protective layer 1 is adopt the mode of vacuum coating by silica-base material evaporation on described lithium powder material layer 21, and the thickness of described silica-based protective layer 1 is 0.02 ~ 0.2 μm.
As shown in Figure 2; because lithium powder porous electrode 2 is powder porous electrode; described silica-based protective layer 1 adopt vacuum coating mode by silica-base material evaporation to described lithium powder material layer 2 time; described silica-based protective layer 1 can enter into lithium metal powder porous between gap; thus penetrate in lithium powder porous electrode 2; thus can better protect lithium anode, prevent it from charge and discharge process, forming Li dendrite, also better compensate for the capacitance loss of plated film negative pole.
The lithium anode of above-mentioned high security adopts following steps to prepare:
By motlten metal lithium and 240 DEG C of hot silicone oil mixed liquors, high-speed stirred under the mixing speed of 28000rpm forms dispersion, then be cooled to room temperature and obtain metallic lithium powder, after cyclohexane washs five times, carry out drying at room temperature, obtaining particle size distribution is 18 ~ 30 μm of metallic lithium powders; Obtained metallic lithium powder and binding agent PVDF is taken respectively according to metallic lithium powder and binding agent PVDF mass ratio 90:10,1.5 times of oxolanes to metallic lithium powder and binding agent PVDF pressed powder quality are injected de-airing mixer, stir 2h and mix slurry, the Copper Foil of anticipating is coated with, dries, compressing tablet prepares lithium powder porous electrode 2; Silica-base material is put into the vacuum chamber of vacuum coating equipment, 10
-2under the vacuum condition of Pa, evaporated by silica-base material, gas ionization atomic deposition forms at substrate surface the silica-based protective layer 1 that thickness is 0.05 μm; The lithium metal powder electrode 2 being coated with silica-based protective layer 1 is made negative pole, and cobalt acid lithium makes positive pole, and electrolyte is the LiPF6/EC+DMC of 1mol/L, prepares high-energy serondary lithium battery, tests.
Through test, the capacity of the serondary lithium battery that this example is obtained is up to 1583mAh/g, and the internal resistance of cell is 9m, and first charge-discharge coulombic efficiency is 95.8%, when capability retention during 10C multiplying power discharging is 1C multiplying power discharging 93.1%, after 500 circulations, reversible capacity is 1152mAh/g.
Embodiment 2
On the basis of embodiment 1, the structure of the lithium anode of the high security of this example is with embodiment 1, and only preparation method is different, and this example adopts following steps to prepare:
By motlten metal lithium and 250 DEG C of hot silicone oil mixed liquors at 30,000 rpm high-speed stirred form dispersion, be cooled to room temperature and obtain metallic lithium powder, drying at room temperature after cyclohexane washs three times, obtaining particle size distribution is 18 ~ 30 μm of metallic lithium powders; Obtained metallic lithium powder and binding agent PVDF is taken respectively according to the mass ratio of metallic lithium powder and binding agent PVDF mass ratio 80:20,2.0 times of oxolanes to metallic lithium powder and binding agent PVDF pressed powder quality are injected de-airing mixer, stir 4h and mix slurry, the Copper Foil of anticipating is coated with, dries, compressing tablet prepares lithium powder porous electrode 2; Silica-base material is put into the vacuum chamber of vacuum coating equipment, 10
-4under the vacuum condition of Pa, evaporated by silica-base material, it is 0.08 μm of silica-based protective layer 1 that gas ionization atomic deposition forms thickness on the surface of lithium powder material layer 21; The lithium metal powder electrode 2 being coated with silica-based protective layer 1 is made negative pole, and cobalt acid lithium makes positive pole, and electrolyte is the LiPF6/EC+DMC of 1mol/L, prepares high-energy secondary cell, tests.
Through test, the capacity of the serondary lithium battery that this example is obtained is up to 1487mAh/g, and the internal resistance of cell is 12m, and first charge-discharge coulombic efficiency is 92.1%, when capability retention during 10C multiplying power discharging is 1C multiplying power discharging 90.4%, after 500 circulations, reversible capacity is 1072mAh/g.
The embodiment of the above is better embodiment of the present utility model; not limit concrete practical range of the present utility model with this; scope of the present utility model comprises and is not limited to this embodiment, and the equivalence change that all shapes according to the utility model, structure are done is all in protection range of the present utility model.
Claims (6)
1. a lithium anode for high security, is characterized in that: comprise lithium powder porous electrode and silica-based protective layer, and described silica-based protective layer evaporation is on described lithium powder porous electrode, and the thickness of described silica-based protective layer is 0.02 ~ 0.2 μm.
2. lithium anode according to claim 1, is characterized in that: the thickness of described silica-based protective layer is 0.04 ~ 0.1 μm.
3. lithium anode according to claim 1 and 2, is characterized in that: described lithium powder porous electrode comprises lithium powder material layer and collector, and described lithium powder material layer is connected with collector.
4. lithium anode according to claim 3, is characterized in that: the particle diameter of described lithium powder is 10 ~ 100 μm.
5. lithium anode according to claim 4, is characterized in that: the particle diameter of described lithium powder is 18 ~ 30 μm.
6. lithium anode according to claim 3, is characterized in that: described collector is Copper Foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201520484709.3U CN204885286U (en) | 2015-07-07 | 2015-07-07 | Lithium metal negative pole of high security |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201520484709.3U CN204885286U (en) | 2015-07-07 | 2015-07-07 | Lithium metal negative pole of high security |
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| CN204885286U true CN204885286U (en) | 2015-12-16 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104966814A (en) * | 2015-07-07 | 2015-10-07 | 李震祺 | High-security metallic lithium cathode and preparation method thereof |
| CN108346776A (en) * | 2018-02-08 | 2018-07-31 | 清华大学 | A kind of composition metal cathode of lithium of sandwich structure and preparation method thereof |
| CN109309234A (en) * | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | Lithium anode, preparation method and the lithium battery comprising the lithium anode |
-
2015
- 2015-07-07 CN CN201520484709.3U patent/CN204885286U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104966814A (en) * | 2015-07-07 | 2015-10-07 | 李震祺 | High-security metallic lithium cathode and preparation method thereof |
| CN109309234A (en) * | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | Lithium anode, preparation method and the lithium battery comprising the lithium anode |
| CN108346776A (en) * | 2018-02-08 | 2018-07-31 | 清华大学 | A kind of composition metal cathode of lithium of sandwich structure and preparation method thereof |
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