CN107565088A - A kind of preparation method of lithium metal secondary battery negative pole - Google Patents
A kind of preparation method of lithium metal secondary battery negative pole Download PDFInfo
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- CN107565088A CN107565088A CN201710569976.4A CN201710569976A CN107565088A CN 107565088 A CN107565088 A CN 107565088A CN 201710569976 A CN201710569976 A CN 201710569976A CN 107565088 A CN107565088 A CN 107565088A
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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
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- 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 is a kind of preparation method of lithium metal secondary battery negative pole.Aluminium foil thick one layer in original lithium anode Surface coating about 600nm of this method, during assembled battery, electrolyte is added dropwise on aluminium foil, electrolyte can react to form lithium-aluminium alloy rapidly with aluminium foil.The present invention can prevent the too high lithium metal of activity from directly contacting generation adverse reaction with electrolyte, reduce in uneven lithium ion deposition process and form Li dendrite, the problem of so as to largely mitigate electrolyte constantly consumption and cathode of lithium heavy corrosion to a certain extent, and then improve the cycle life of battery.
Description
Technical field
It is secondary more particularly to a kind of lithium metal that negative pole protection is made of aluminium foil the present invention relates to the negative pole containing lithium metal
Battery and its design method, belong to battery technology association area.
Background technology
Since 21 century, because people are further increasing the demand of conventional fossil fuel so that fossil fuel
Price gradually grow, and the environmental pollution as caused by the burning of fossil fuel and greenhouse effects are also more serious.So seek new
The environmentally friendly energy of type sustainable development is extremely urgent.And novel secondary battery and its associated materials field are just such
Arisen at the historic moment under dual background.Lithium ion battery (LIBs) can have high energy compared to other for secondary cell of discharge and recharge
Metric density, therefore be the most frequently used electrochemical storage device and widely to be studied at present.Currently, it is widely used in portable electric
Lithium ion battery in sub- product is considered as the prioritizing selection of energy storage and electrical source of power.But with Portable electric automobile
And the fast development of electronic equipment, traditional LIBs (120-170Wh kg-1) it is impossible to meet in practical application to high-energy
The requirement of density, so a new generation has the novel energy storage apparatus of high-energy-density there is an urgent need to be developed, in consideration of it, I
Devise and a kind of new do the lithium ion battery structure that negative pole protects with aluminium foil and increase its energy density.
Traditional LIBs includes several part and parcels, positive and negative pole material, both positive and negative polarity collector, electrolyte, barrier film.Although stone
Ink, which has proved to be, to be used to make the best of negative electrode and most reliable material so far, but the amount of ions that it is accommodated is limited.Grind
Study carefully personnel to wish to substitute graphite with lithium metal always, it can accommodate more ions, and lithium metal has high theoretical appearance
Measure (3860mAh g-1) and minimum negative potential (being -3.04V relative to standard hydrogen electrode), but usual lithium metal activity is too
Height, is particularly easy to produce adverse reaction with electrolyte, and SEI films are formed on Li surfaces, when virtually limitless in lithium stripping deposition process
Volume Changes, so as to cause the heavy damage of the SEI films of fragility and mechanical instability, produce crack, crack local enhancement Li
By, can produce dendrite in the opening position of current density local enhancement, in charge and discharge process, it is high must specific surface area Li branches
Brilliant and SEI films continuous destruction reparation brings ceaselessly side reaction, cause electrolyte constantly consume with cathode of lithium heavy corrosion,
So as to the cycle life of serious curtailment battery.So the dendrite problems solved in lithium an- ode cyclic process turn into current electricity
A major challenge of pond research field.Thus, it is that lithium metal secondary cell is applied with developing to suppress the formation of Li dendrite and growth
One of serious problems for urgently solving are needed in journey.
In the prior art, for protecting negative pole, solving the method for Li dendrite has a lot, as carried in patent CN106252722A
A kind of electrolysis additive with dual Li dendrite inhibitory action is gone out, Li dendrite is inhibited in terms of two in electrode surface
Formation, first, improving the wellability of electrolyte and barrier film by reducing electrolyte surface tension force, increase lithium ion is in barrier film
In transmission channel so that lithium ion stream is uniformly distributed in electrode surface, is finally reached and suppresses the purpose that Li dendrite is formed；Its
Two, additive further improves deposition site of the lithium ion in electrode surface by being adsorbed in electrode surface, so as to suppress lithium branch
Crystalline substance is formed.In addition, patent CN105789704A provide a kind of nonaqueous solvents for suppressing Li dendrite, nonaqueous electrolytic solution (it is a kind of or
Two or more carbonic ethers and one or more kinds of specific amine), it can effectively press down in lithium rechargeable battery
Make the growth of the Li dendrite caused by charging.In addition, patent CN103531839A discloses one kind and prevents Li dendrite
Fill lithium metal secondary battery, the battery system is made up of lithium salts, nonaqueous solvents and/or electrolysis additive, pass through choose close
It is fit to be and salt in system and solvent burden ratio are modulated, so as to change the things such as electrolyte solvates lithium ions degree and viscosity
Physicochemical performance and in electrochemical process solid interphase film caused by metallic lithium surface physical and chemical performance, and then
Effectively suppress the growth of negative metal lithium surface dendroid Li dendrite caused by electrochemical deposition is uneven, finally play
The purpose of lithium metal secondary battery security performance can be filled by improving.Nanjing University Zhu Jia professor (Advanced Material,
2017,29,1603755, DOI：10.1002/adma.201603755) propose with common cheap poly dimethyl silicon
Oxygen alkane (PDMS) is used as lithium anode protective layer.PDMS has separated lithium metal and electrolyte well, stabilizes interface, suppression
The growth of Li dendrite processed.The lithium anode protected by PDMS, the circulation coulomb stabilised efficiency of 200 times in half-cell test
There is a certain distance in 95% or so (conventional lithium-ion battery electrolyte), but with commercialization and practical application.In summary,
Technology is all to suppress negative pole SEI growth using electrolyte mostly above, so as to play a part of protecting negative pole.But mesh
Before untill most of additive be all to be improved or the formation of dendrite inhibition by participating in forming diaphragm, and such additives
It can typically weaken with the increase of cycle-index.
The content of the invention
It is an object of the invention to overcome the shortcomings of prior art, it is proposed that one kind does negative pole and negative current collector with aluminium foil
Lithium metal secondary battery and its design method.One layer in original lithium anode Surface coating about 600nm of this method is thick
Aluminium foil, during assembled battery, be added dropwise electrolyte on aluminium foil, electrolyte can be reacted rapidly with aluminium foil to be formed lithium aluminium conjunction
Gold.Prevent the too high lithium metal of activity from directly contacting generation adverse reaction with electrolyte, reduce uneven lithium ion deposition
During form Li dendrite, asked so as to largely mitigate electrolyte constantly consumption and cathode of lithium heavy corrosion to a certain extent
Topic, and then improve the cycle life of battery.
The technical scheme is that：
A kind of preparation method of lithium metal secondary battery negative pole, comprises the following steps：
1) Kynoar (PVDF) powder is dissolved in 1-METHYLPYRROLIDONE (NMP), it is 40-50mg mL to obtain concentration-1
Solution, ie in solution one；
2) by LiFePO4Added with Ketjen black (KB) in ball grinder, then solution one and NMP be added dropwise successively, then ball milling 3~
5h, slurry one is made；
Wherein, mass ratio LiFePO4：Ketjen black (KB)：The 8 of PVDF：1：1；Per LiFePO432mg adds 2-5mL NMP；
3) electrode slice is made coated on Al paper tinsel collectors in slurry one；Coating thickness is 200-300 μm；
4) electrode slice that upper step obtains is placed in vacuum drying chamber, 85-95 DEG C is heated overnight, and is then naturally cooling to room
Temperature；
5) electrode slice after drying is cut into a diameter of 7-12mm pole piece；
6) aluminium foil is cut out：The thick aluminium foils of 550-650nm are cut into slitter a diameter of 16-19mm disk, 30-40 DEG C true
Sky is dried, and Temperature fall, it is standby to be put into glove box；
7) in glove box, obtain aluminium foil disk with step and cover the front of lithium piece, then the two is compacted, obtains gold
Belong to lithium secondary battery anode；Wherein, aluminium foil disk is identical with the diameter of lithium piece, is 16-19mm；
8) battery assembles：It is positive pole by 5) gained pole piece, Celgard 2400 is barrier film, is electrolyte, is made in step 7)
The lithium metal of the aluminium foil cladding obtained is negative pole, and the button cells of CR 2032 are assembled into the glove box full of argon atmosphere；
Described electrolyte is one of two kinds of solution, and the first is 1M LiPF6Solution, its solvent are ethylene carbonate
(EC) and diethyl carbonate (DEC) mixed liquor, the volume ratio of the two be 1:1, or second, contain LiPF6(carbonic acid is sub- with VC
Vinyl acetate) solution, wherein, solvent is the mixed liquor of ethylene carbonate (EC) and diethyl carbonate (DEC), the volume ratio of the two
For 1:1；LiPF6Concentration be 1M, VC mass is the 5% of the quality of solution；
Comprise the following steps：A shell fragment is put into negative electrode casing, shell fragment is placed above a pad, placed on pad
The metal lithium sheet of the Surface coating aluminium foil of gained in 8,2-3 drops electrolyte is added dropwise in aluminium foil surface, then puts a Celgard
2400 barrier films, in terms of positive electrode is placed on barrier film, anode cover is finally buckled, is encapsulated with packaging machine, is assembled into button cell.
The beneficial effect of this lithium an- ode protection invention is：
In the lithium metal secondary cell in original cathode of lithium Surface coating one layer of 600nm aluminium foil, they are common to make
For negative pole, extremely just LiFePO4, in charging process, lithium ion is from LiFePO4Middle abjection, by electrolyte, through barrier film, turn
Aluminium foil negative pole is moved on to, forms LiAl alloys and SEI films, on the contrary, during electric discharge, lithium ion is from LiAl alloy materials by taking off alloy
Process, LiFePO is transferred to by electrolyte4Positive pole.Unlike conventional lithium ion battery, after cathode of lithium cladding aluminium foil,
Electrolyte is added dropwise, one layer of LiAl alloy firm can be formed by alloying reaction in charge and discharge process, alleviate high activity
Lithium metal Direct Electrolysis liquid contact produce adverse reaction, reduce in uneven lithium ion deposition process and form Li dendrite, and
It is to form LiAl alloys on Al paper tinsels surface.It is seriously rotten so as to largely mitigate electrolyte constantly consumption and cathode of lithium to a certain extent
Erosion, and then improve the cycle life of battery.In this patent, with commercialized material ferric lithium phosphate (LiFePO4) it is positive pole, lead to
The lithium metal crossed the lithium anode to having coated aluminium foil and do not coat aluminium foil does negative pole performance and made comparisons, and finds the protection of aluminium foil
So that the cycle performance of battery is further improved.Moreover, use optimization, after suitable electrolysis additive, performance
More it is significantly improved.In order to verify that the negative pole of aluminium foil cladding inhibits the generation of Li dendrite, after we are to the circle of circulation 50
Battery is studied.Battery after the circle of circulation 50 is taken apart in glove box, lithium piece is taken out, then by it in glove box transition
Vacuumize process in cabin, the residual component on its surface is set to volatilize completely.Lithium piece is transferred in Electronic Speculum with sealing container afterwards and seen
Examine.It was found that having the lithium metal that aluminium foil coats compared with no aluminium foil, surface is more smooth, illustrates that the cladding of aluminium foil inhibits lithium
The generation of dendrite, so as to which the security of lithium metal secondary cell be greatly improved.In this patent, negative pole protection is done with aluminium foil, added
In the case of adding electrolysis additive VC, first circle efficiency is 99.6%, charging capacity 141.8mAh g-1Charging capacity 141.2mAh
g-1, the circle capacity of circulation 50 is up to 141.5mAh g-1。
Brief description of the drawings
Fig. 1 is the cycle life that this patent makes the enhancing battery that negative pole is protected of aluminium foil so that the security performance of battery is more
Add good.Lithium metal battery structural representation.Wherein, 1- negative electrode casings；2- spring leafs；3- pads；4- metal lithium sheets；5-600nm
Aluminium foil；6-Celgard-2400 barrier films；7- positive electrodes；8- anode covers；
The battery charging and discharging curve that Fig. 2 is assembled by embodiment 1.
Fig. 3 tears battery surface SEM patterns open by embodiment 1.
The battery charging and discharging curve that Fig. 4 is assembled by embodiment 3.
Fig. 5 tears battery surface SEM patterns open by embodiment 3.
The battery charging and discharging curve that Fig. 6 is assembled by comparative example 1.
Fig. 7 tears battery surface SEM patterns open by comparative example 1.
The battery charging and discharging curve that Fig. 8 is assembled by comparative example 2.
Embodiment
The present invention is described further with reference to embodiment.
Embodiment 1：
A kind of aluminium foil does the preparation method of the lithium metal secondary battery of negative pole protection, and step is as follows：
1) 32mg LiFePO are weighed4For powder as positive electrode active materials, 4mg Ketjen blacks are conductive agent, and 80uL, dense
Spend for 50mg mL-1Kynoar (PVDF) solution (solvent is 1-METHYLPYRROLIDONE (NMP)) be used as binding agent, be added dropwise
As dispersant the ball milling 5h in ball grinder, slurry one is made in 3ml NMP；
2) slurry one is uniformly coated in positive (the i.e. matt of one side optical aluminum foil of the collector that scrubs with hymenotome is scraped
Face, thickness are 16 ± 2um, and Ke Jing companies buy).Electrode slice is made, coating thickness is 200 μm, and 90 DEG C are dried in vacuum overnight simultaneously
Temperature fall；
3) electrode slice for drying simultaneously Temperature fall is cut into a diameter of 10mm pole piece with slitter.
4) through measurement, the active material carrying capacity on the pole piece that upper step obtains is about 2.5mg cm-2；
5) aluminium foil is cut out：The thick aluminium foils of 600nm being cut into slitter a diameter of 16mm disk, 30-40 DEG C is dried in vacuo,
Temperature fall, it is standby to be put into glove box；
6) in glove box, front of the aluminium foil disk (16mm) lithium piece (diameter 16mm, thickness 0.2mm) is obtained with step
The two, is then compacted, obtains lithium metal secondary battery negative pole by covering；
7) battery assembles：It is positive pole by 4) gained pole piece, Celgard 2400 is barrier film, and electrolyte is 1M LiPF6(EC：
DEC=1:1) lithium metal, coated with 600nm aluminium foil is that negative pole is assembled into CR in the glove box full of argon atmosphere
2032 button cells, electro-chemical test is carried out with LAND.
8) lithium piece surface SEM is tested：Battery after the circle of circulation 50 is taken apart in glove box, takes out lithium piece, then will
Its vacuumize process in glove box transfer chamber, makes the residual component on its surface volatilize completely.Afterwards with sealing container by lithium piece
It is transferred in Electronic Speculum and observes.
The assembling of lithium metal battery described in example one is as shown in figure 1, method is the group in the glove box full of argon atmosphere
Packed battery model CR 2032 button lithium metal battery.This method is known technology, is summarized as follows：Full of argon atmosphere
Glove box in, according to described in Fig. 1 will 1. negative electrode casing, 2. shell fragment, 3. pad (a diameter of 16mm), 4. lithium piece is (a diameter of
16mm), 5. 600nm aluminium foil, 6. barrier film (barrier film is completely separated both positive and negative polarity here by Celgard 2400, a diameter of 19mm,
19mm so necessarily bigger than the diameter of lithium piece), 7. positive electrode (LiFePO4), 8. anode cover order assembling button electricity
Pond, wherein, all need that 2-3 drop electrolyte (LiPF is added dropwise before and after barrier film is placed6(EC：DEC=1:1)) in aluminium foil table
Face, aluminium foil become grey with the lithium metal alloying reaction in situ that occurs, and obtained battery stands 2~10 small in surrounding air
When, using LAND battery test systems in room temperature (25 ± 2 DEG C) surrounding air, battery 2.0-3.8V voltage range,
100mA g-1Current density under carry out charge-discharge test, obtain Fig. 1 charge and discharge cycles curve, cycle charge-discharge 50 encloses.Fig. 2
The circulating battery curve map assembled by embodiment 1.Abscissa represents specific capacity, and unit is mAh g-1, ordinate represents voltage,
Unit is V, the 1st circle in figure, the 2nd circle, the data of the charging and discharging of the number of turns where curve corresponding to the 50th circle represents respectively.
Lithium piece surface SEM is tested：Battery after the circle of circulation 50 is taken apart in glove box, lithium piece is taken out, then by it
The vacuumize process in glove box transfer chamber, the residual component on its surface is set to volatilize completely.Lithium piece is turned with sealing container afterwards
Move on in Electronic Speculum and observe.
Embodiment 2
A kind of aluminium foil does the preparation method of the lithium metal secondary battery of negative pole protection, and step is as follows：
Step 1) is same as Example 1；
2) it is 300 μm to change coating thickness, and other conditions are constant；
3) it is same as Example 1；
4) electrode slice is chosen, control active material carrying capacity is about 3.0mg cm-2
5) remaining step is similar with embodiment, and obtained charge and discharge cycles curve and embodiment 1 is similar.
Embodiment 3
Step 1) -4) it is same as Example 1；
5) battery assembles：4) gained pole piece is positive pole, and Celgard 2400 is barrier film, LiPF6(EC：DEC=1:1)+5%
VC (vinylene carbonate) is electrolyte, and the lithium metal coated with 600nm aluminium foil is negative pole in the gloves full of argon atmosphere
The button cells of CR 2032 are assembled into case, electro-chemical test is carried out with LAND, the Integration Assembly And Checkout method of battery with embodiment 1,
Obtained charge and discharge cycles curve is as shown in Figure 4.
Embodiment 4
Step 1) -4) it is same as Example 2；
5) battery assembles：4) gained pole piece is positive pole, and Celgard 2400 is barrier film, LiPF6(EC：DEC=1:1)+5%
VC (vinylene carbonate) is electrolyte, and the lithium metal coated with 600nm aluminium foil is negative pole in the gloves full of argon atmosphere
The button cells of CR 2032 are assembled into case, electro-chemical test is carried out with LAND.
Remaining step and embodiment 1 are similar, and obtained charge and discharge cycles curve and embodiment 3 is similar.
Comparative example 1：
Step 1) -4) it is similar with embodiment 1；
5) battery assembles：It is positive pole by 4) gained pole piece, Celgard 2004 is barrier film, LiPF6(EC：DEC=1:1) it is
Electrolyte, it is that negative pole is assembled into the button cells of CR 2032 in the glove box full of argon atmosphere directly with lithium metal, uses LAND
Carry out electro-chemical test；
6) remaining step and embodiment 1 are similar, and obtained charge and discharge cycles curve is as shown in Figure 5.
Comparative example 2：
Step 1) -4) it is similar with embodiment 1；
5) battery assembles：It is positive pole by 4) gained pole piece, Celgard 2004 is barrier film, LiPF6(EC：DEC=1:1)+
5%VC (vinylene carbonate) is electrolyte, and the lithium metal coated with 600nm aluminium foil is negative pole in the hand full of argon atmosphere
The button cells of CR 2032 are assembled into casing, electro-chemical test is carried out with LAND；
6) remaining step and embodiment 1 are similar, and obtained charge and discharge cycles curve is as shown in Figure 6.
The embodiment 1,3 of table 1 contrasts with battery performance in comparative example 1,2
It was found from Fig. 2 and Fig. 6 contrasts, in the case where not adding electrolysis additive VC, negative pole protection is done with aluminium foil, gold
Belong to lithium secondary battery, first circle efficiency is 92.3%, charging capacity 128.4mAh g-1, discharge capacity 118.6mAh g-1, circulation 50
Capacity is enclosed up to 120.2mAh g-1, performance is better than comparative example 1, the battery (Fig. 6) of negative pole directly made of lithium metal.
It was found from Fig. 4 and Fig. 8 contrasts, negative pole protection is done with aluminium foil, in the case of adding electrolysis additive VC, first circle effect
Rate is 99.6%, charging capacity 141.8mAh g-1Charging capacity 141.2mAh g-1, the circle capacity of circulation 50 is up to 141.5mAh g-1.Performance is better than comparative example 1 and comparative example 2, directly makees the battery of negative pole with lithium metal and is not added with the battery of electrolysis additive.
Further contrasted from Examples 1 and 2, the SEM shape appearance figures of comparative example 1, it can be seen that lithium piece surface is more flat after having added aluminium foil
It is whole, the appearance of Li dendrite is hardly visible, largely mitigation electrolyte is continuous to a certain extent so doing negative pole protection with aluminium foil
Consumption and cathode of lithium heavy corrosion, and then strengthen the cycle life of battery so that the security performance of battery is better.
Unaccomplished matter of the present invention is known technology.
Claims (3)
- A kind of 1. preparation method of lithium metal secondary battery negative pole, it is characterized in that this method comprises the following steps：1）By Kynoar（PVDF）Powder is dissolved in 1-METHYLPYRROLIDONE（NMP）, it is 40-50 mg mL to obtain concentration-1's Solution, ie in solution one；2）By LiFePO4And Ketjen black（KB）Add in ball grinder, then solution one and NMP are added dropwise successively, then the h of ball milling 3 ~ 5, system Into slurry one；Wherein, mass ratio LiFePO4：Ketjen black（KB）：The 8 of PVDF：1：1；Per LiFePO432 mg add 2-5 mL NMP；3）By slurry one coated on Al paper tinsel collectors, electrode slice is made；Coating thickness is 200-300 μm；4）The electrode slice that upper step obtains is placed in vacuum drying chamber, 85-95 DEG C is heated overnight, and is then naturally cooling to room temperature；5）Electrode slice after drying is cut into a diameter of 7-12 mm pole piece；6）Cut out aluminium foil：The thick aluminium foils of 550-650 nm are cut into slitter a diameter of 16-19 mm disk, 30-40 DEG C of vacuum Dry, Temperature fall, it is standby to be put into glove box；7）In glove box, obtain aluminium foil disk with step and cover the front of lithium piece, then the two is compacted, obtains lithium metal Secondary battery negative pole；Wherein, aluminium foil disk is identical with the diameter of lithium piece, is 16-19 mm；8）Battery assembles：By 5）Gained pole piece is positive pole, and Celgard 2400 is barrier film, is electrolyte, step 7）In it is obtained The lithium metal of aluminium foil cladding is negative pole, and secondary cell is assembled into the glove box full of argon atmosphere.
- 2. the preparation method of lithium metal secondary battery negative pole as claimed in claim 1, it is characterized in that described electrolyte is two One of kind solution, the first is 1M LiPF6Solution, its solvent are ethylene carbonate（EC）And diethyl carbonate（DEC）It is mixed Liquid is closed, the volume ratio of the two is 1:1, or second, contain LiPF6And VC（Vinylene carbonate）Solution, wherein, solvent For ethylene carbonate（EC）And diethyl carbonate（DEC）Mixed liquor, the volume ratio of the two be 1:1；LiPF6Concentration be 1M, VC mass is the 5% of the quality of solution.
- 3. the preparation method of lithium metal secondary battery negative pole as claimed in claim 1, it is characterized in that described battery assembling Step includes：A shell fragment is put into negative electrode casing, a pad is placed above in shell fragment, and the table of gained in 8 is placed on pad The metal lithium sheet of bread cladded aluminum foil, 2-3 drops electrolyte is added dropwise in aluminium foil surface, then puts a barrier film of Celgard 2400, In terms of positive electrode is placed on barrier film, anode cover is finally buckled, is encapsulated with packaging machine, is assembled into button cell.
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| CN110265654A (en) * | 2019-05-16 | 2019-09-20 | 同济大学 | A kind of negative electrode of lithium ion battery ultrathin lithium silver alloy band and preparation method thereof |
| CN110364686A (en) * | 2019-07-15 | 2019-10-22 | 湖北锂诺新能源科技有限公司 | The production method of button type lithium-manganese battery cathode can be filled |
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| CN111952571A (en) * | 2020-08-24 | 2020-11-17 | 上海空间电源研究所 | Lithium/lithium alloy composite negative electrode for high-power primary battery, preparation method and battery |
| CN112802997A (en) * | 2021-02-24 | 2021-05-14 | 华南理工大学 | Lithium metal battery with curved surface lithium piece negative pole |
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|---|---|
| CN107565088B (en) | 2021-01-08 |
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