CN1360356A - Foam-metal current collector of secondary battery using zinc as negative electrode and its preparing process - Google Patents
Foam-metal current collector of secondary battery using zinc as negative electrode and its preparing process Download PDFInfo
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- CN1360356A CN1360356A CN02100408A CN02100408A CN1360356A CN 1360356 A CN1360356 A CN 1360356A CN 02100408 A CN02100408 A CN 02100408A CN 02100408 A CN02100408 A CN 02100408A CN 1360356 A CN1360356 A CN 1360356A
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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 invention relates to a method for preparing foam metal current collector (substrate) of new type secondary battery that uses zinc as negative pole. It possesses foamy space structure whose space cellular structure in three dimension is composed of metal framework connected eath other. Its surface ingredient includes copper 68%-75% (Wt), zinc 32-25%, that is copper-zinc alloy or foamy brass. The collector (substrate) being as zinc pole has very good performance in electrochemistry and better circular performance. The invention possesses merits of stable characteristic, low cost, simple technique, lower relative density, good electrical conductivity etc. The invention is particularly suitable for zinc-nickel secondary battery, also other zinc based secondary battery and alkaline secondary battery.
Description
Affiliated technical field
The present invention relates to secondary cell, particularly a kind of being used for zinc is the preparation of novel foam brass collector (matrix) of secondary cell of negative pole.
Background technology
Along with The development in society and economy, the raising of environmental consciousness, people more and more need a kind of high-energy-density, high power, low price, free of contamination electrical source of power in the new century.And zinc-nickel secondary batteries can satisfy people's needs just, thereby zinc-nickel secondary batteries becomes the focus of research and development again.
Compare with ni-mh, NI-G, lead-acid battery, zinc-nickel cell has outstanding advantage: and (1) specific energy height (theoretical value 326Wh/kg, actual value 〉=75Wh/kg); (2) specific power big (〉=200W/kg); (3) operating temperature range wide (20 ℃～60 ℃); (4) operating voltage height (1.65V); (5) efficiency for charge-discharge height (〉=80%); (6) high rate during charging-discharging is better; (7) wet shelving performance is better; (8) cost is low, pollution-free etc.Thereby zinc-nickel cell obtains various countries scientist's extensive concern in recent years, and zinc-nickel cell is studied as electrokinetic cell from the beginning.The subject matter of restriction zinc-nickel cell practical application is that zinc electrode cycle life is shorter at present; Easily produce a large amount of gases in the use.The reason that produces these problems is that zinc electrode exists phenomenons such as deformation, dendrite, corrosion and passivation.
Collector (matrix) is the necessary parts of zinc-nickel secondary batteries.In zinc-nickel cell, because the zinc in the solution need be with collector (matrix) as depositing matrix to store active material when charging, therefore the character of collector (matrix) will be directly connected to zinc on collector (matrix) deposition and the charge status of battery, thereby phenomenons such as zinc electrode deformation, dendrite, corrosion and passivation are made a difference, and then the cycle life of zinc-nickel cell is produced conclusive effect.
Collector (matrix) commonly used comprises nickel wire net, punching nickel strap, nickel foam etc. in alkaline secondary cell at present.Especially nickel foam because it has advantages such as favorable conductive and binding ability, specific surface are big, to hold active material many, and chemical property is stable, at alkaline secondary cell, particularly is widely used in NI-G and Ni-MH battery.But experiment shows that alkaline secondary cell collectors (matrix) commonly used such as nickel wire net, punching nickel strap, nickel foam all are not suitable for zinc-nickel cell.Present relative performance zinc-nickel cell preferably all uses precious metals silver as collector (matrix), and present studies show that, common elemental metals all can't replace silver as zinc-nickel cell collector (matrix).The price that silver is expensive has seriously limited promoting the use of of zinc-nickel cell, thus find a kind of novel, low price, performance better, collector (matrix) that practicability is stronger, be the basis of zinc-nickel cell practicability and crucial.
Summary of the invention
Purpose of the present invention aim to provide a kind of novel be the foam-metal current collector body and preparation method thereof of the secondary cell of negative pole with zinc, it has overcome the shortcoming of prior art, it is silver-colored collector of a kind of good generation (matrix), it is mainly used in zinc-nickel cell, also can be applied to other zinc-base secondary battery and alkaline secondary cell simultaneously.
Foam-metal current collector body of the present invention (matrix), its surface composition is a brass: promptly cupric 68%～75%, the ormolu that contains zinc 32～25%, the thickness of layer of brass is 0.01 μ m～1000 μ m, its structure is for having foamed space three-dimensional structure, interconnective metallic framework constitutes three-dimensional space network structure, forms a large amount of cavernous structures and can be used for filling active material, has very high porosity.Thereby foam-metal current collector body of the present invention (matrix) also can be called foamed brass.
The preparation method of foam-metal current collector body of the present invention (matrix) foamed brass has following several:
(1), be that the foamed sheet of 0.1mm～10mm is through overactivation, sensitization, at Cu salt/EDTA/ methyl alcohol/NiCl with thickness 1)
2Solution system in, be reducing agent with formaldehyde or inferior sodium phosphate, carry out electroless copper.The pH value of solution value is 7～14, and reaction temperature is 20～80 ℃, and the reaction time is 0.3～10 hour.2) will carry out the foamed sheet of electroless copper, in resistance furnace, carry out high-temperature process, during processing with Ar, N
2, H
2One or more gaseous mixtures in the gas are protected, and treatment temperature is 200～1000 ℃, and the processing time is 0.3～10 hour.Obtain foam copper after the processing.3) foam copper is electroplated layer of copper, thereby play ruggedized construction, the effect of surface evening.4) with foam copper brass plating in the solution system of Cu salt/Zn salt/potassium pyrophosphate/glycerine/oxalic acid/dipotassium hydrogen phosphate.Anode is brass or copper coin+zine plate or inert metal, and cathode-current density is 0.01～10A/dm
2, the pH value of solution value is 7～14, and electroplating temperature is 20～80 ℃, and electroplating time is 1～120 minute, and thickness of coating is 0.01 μ m～1000 μ m.Obtain foamed brass after the plating.Use glycerine to make additive and not only can in pyrophosphate tank liquor system, obtain satisfied brass coating, and in tank liquor systems such as cyanide salt, cyanide salt+pyrophosphate, HEDP, ethylenediamine, carbonate, rhodanate, sulfate, oxalates, tartaric acid, triethanolamine, thiosulfate, chlorate+thiosulfate, ferrocyanide, formamide, also all can obtain satisfied brass coating.
(2), will be by in (one) 2) or 3) the resulting foam copper of step, electroplate layer of copper earlier, after ethylenediamine solution was handled, re-plating one deck zinc carried out high-temperature process then, during processing with Ar, N
2, H
2One or more gaseous mixtures in the gas are protected, and treatment temperature is 200～1000 ℃, and the processing time is 0.3～10 hour.Also obtain foamed brass after the processing.
(3), in other foam metal matrix (as nickel foam, foamed aluminium, foam lead, foam silver etc.) is gone up according to (one) 4) or the method for (two) handle, also can obtain foamed brass.
(4), will carry out annealing in process or surface treatment by (one) or (two) or (three) resulting foamed brass.Ar, N during annealing
2, H
2One or more gaseous mixtures in the gas are protected, and annealing temperature is 200～1000 ℃, and annealing time is 0.3～100 hour.Surface treatment comprises chemistry or electrochemical polish, element replacement etc.
Annotate: step () 3) and (four) can omit.
Foam-metal current collector body of the present invention (matrix) foamed brass has very excellent in performance as zinc-nickel cell collector (matrix).Foamed brass has stable chemical property and electrochemical properties in alkaline electrolyte; The zinc electrode that with the foamed brass is collector (matrix) has high overpotential of hydrogen evolution, positive corrosion potential, little corrosion electric current density, little anode polarization, has obviously improved the corrosive nature of zinc electrode; Be the supersaturation that the zinc electrode of collector (matrix) has reduced electrolyte to a certain extent with the foamed brass, suppressed the deformation phenomenon of zinc electrode; The zinc electrode that with the foamed brass is collector (matrix) has extraordinary invertibity; It with the foamed brass growth that the zinc electrode of collector (matrix) has suppressed dendrite; The zinc electrode that with the foamed brass is collector (matrix) has good discharge performance and high cycle life; The foamed brass cost is low, technology is simple, proportion is little, good conductivity, and porosity is big, the unit are hole count is many, pliability good.In general, foamed brass is a kind of very outstanding zinc-nickel cell collector (matrix), can substitute silver-colored collector (matrix) ideally, and the invention of foamed brass is that the practicability of zinc-nickel cell is laid a good foundation.
Because novel foam metal collector of the present invention (matrix) foamed brass has very excellent in performance, thereby the use of foamed brass collector (matrix) can significantly improve the performance of other zinc-base secondary battery and other alkaline secondary cell equally, so foamed brass is a kind of very outstanding collector (matrix) of other zinc-base secondary battery and alkaline secondary cell.
Description of drawings
Fig. 1 is the XRD spectra of foam copper and foamed brass; Fig. 2 is the SEM photo of foamed brass; Fig. 3 is to be the zinc negative discharge capacity～cyclic curve figure of collector with nickel foam and foamed brass.
Embodiment
The present invention is described further below by embodiment:
Embodiment 1 is with the foamed plastics agreement that contracts a film or TV play to an actor or actress 10cm of thick 2mm
2Through SnCl
2Sensitization, 250ml10g/lCuSO is put in silver-colored ammonia complex liquid activation
4.5H
2O+30g/lEDTA+5ml/l methyl alcohol, pH value are in 12.5 the solution, and constant temperature to 35 ℃ drips under about 200 rev/mins stirring condition and contains 1.5gNiCl
2.6H
2The solution of O and 5ml formaldehyde reacted about 1 hour, took out the foamed sheet through electroless copper, cleaned, and dried.To place tube type resistance furnace through the foamed sheet of electroless copper, with Ar+H
2The gaseous mixture protection is warming up to 750 ℃, and cooling obtains foam copper.Foam copper is made negative electrode, place 225g/lCuSO
4.5H
2O+60g/lH
2SO
4In the electroplate liquid of+35g/l glucose, be anode, stir that cathode-current density is 60mA/cm with about 80 rev/mins speed with the copper sheet
2(being apparent area) at room temperature electroplated 20 minutes.Foam copper plays the effect of ruggedized construction and surface evening after electro-coppering.To do the XRD test and (see Fig. 1 a) through adding foam copper multiple and leveling.Foam copper is made negative electrode, place 35g/lZnSO
4.7H
2O+6.8g/lCuSO
4.5H
2O+267g/lK
4P
2O
7.3H
2O+26g/lK
2HPO
4.3H
2O+2.8g/lH
2C
2O
4+ 10ml/l glycerine, pH value are in 8.5 the electroplate liquid, and constant temperature to 35 ℃ is anode with the brass screen, stirs with about 130 rev/mins speed, and cathode-current density is 150mA/cm
2(being apparent area) electroplated 30 minutes, obtained foamed brass.With foamed brass at 10%HNO
3/ 54%H
3PO
4/ 30%CH
3COOH/6%H
2About 20 seconds of chemical polishing under the room temperature in the polishing fluid of O (percent by volume).Foamed brass after the polishing is carried out XRD (seeing Fig. 1 b) and SEM (see figure 2) test sign.From Fig. 1 a as can be seen, through electroless copper and high-temperature process and to reinforce the resulting foam copper of leveling surface through electro-coppering be very pure elemental copper.As can be seen, the foamed brass surface after brass plating and polishing is very pure brass phase, and has covered copper fully from Fig. 1 b.As can be seen from Figure 2, the foamed brass after brass plating and polishing has complete space three-dimensional network structure, and metallic framework is connected with each other, and forms suitable hole, a large amount of apertures, can fill more active material, and the surface is very bright and clean.
Embodiment 2:
Will be by the prepared foamed brass of embodiment 1 as collector (matrix), electrogalvanizing prepares zinc electrode in saturated zincate solution.The oil removing 5min in acetone of elder generation is then at 20mA/cm
2Under the current density, cathodic polarization 1min in 5M KOH solution.At last at saturated zincate solution with current density I=100mA/cm
2, electroplating time t=10min, electrodeposition temperature T=40 ℃ condition electrogalvanizing.Cu, Ni, In, Ag, Zn collector by the same procedure electrogalvanizing, are done electrochemical property test and compared, and the gained data are listed in table 1, as can be seen from Table 1:
The different collectors of table 1 (matrix) are gone up the electrochemical reaction parameter of zinc-plated electrode
| Collector (matrix) | E corr(matrix)/V | ??E corr/V | ?i corr/mA/cm 2 | ??b a/mV | ????E p/V |
| ????Ni | ????-0.960 | ????-1.362 | ????5.976 | ????40.7 | ????-1.281 |
| ????Zn | ????-1.374 | ????-1.417 | ????0.109 | ????34.4 | ????-1.205 |
| ????Cu | ????-0.943 | ????-1.370 | ????2.761 | ????33.1 | ????-1.287 |
| ????Ag | ????-1.027 | ????-1.404 | ????0.567 | ????38.8 | ????-1.288 |
| ????In | ????-1.016 | ????-1.388 | ????1.840 | ????34.2 | ????-1.297 |
| Foamed brass | ????-1.042 | ????-1.393 | ????0.737 | ????34.0 | ????-1.297 |
The corrosion potential E of collector (matrix) own
Corr(matrix) is by arranging by forward is negative: Cu＞Ni＞In＞Ag＞foamed brass＞Zn
Zinc electrode corrosion potential E
CorrBy arranging: Ni＞Cu＞In＞foamed brass＞Ag＞Zn by forward is negative
Zinc electrode corrosion electric current density i
CorrAscending: Zn＜Ag＜foamed brass＜In＜Cu＜Ni
Zinc electrode polarization b
aAscending: Cu＜foamed brass＜In＜Zn＜Ag＜Ni
Zinc electrode causes blunt current potential E
pArrange by forward is negative: Zn＞Ni＞Cu＞Ag＞foamed brass＞In
As can be seen, be that the character of zinc electrode of collector (matrix) is similar to the zinc electrode that is collector (matrix) with the foamed brass with Ag, every character all belongs between two parties basically, comparatively balance.In general, be that the character of zinc electrode of collector (matrix) is very outstanding with the foamed brass, foamed brass is a silver-colored collector of a kind of desirable generation (matrix).
Embodiment 3
To be made comparisons by the prepared foamed brass of embodiment 1 and brass screen and secondary cell collector (matrix) nickel foam commonly used, research is the zinc electrode dendritic growth situation of collector (matrix) with them.In saturated zincate solution, respectively foamed brass, brass screen and three kinds of collectors of nickel foam (matrix) are added-overpotential of 100mV constant potential polarization 4500 seconds.When dendritic growth, will increase the surface area of zinc electrode greatly, thereby the total current of zinc electrode is increased.Judge the upward growing state of zinc dendrite of collector (matrix) according to the growth rate of total current.The zinc electrode total current added value and the growth rate of three kinds of collectors (matrix) see Table 2.
Table 2 constant potential (100mV) the total current increase value of the last deposition zinc of different collectors (matrix) under the condition
| Foamed brass | Brass screen | Nickel foam | |
| ?I(t＝0s)/mA | ????70 | ????59 | ????95 |
| ?I(t＝4500s)/mA | ????168 | ????207 | ????260 |
| ?I(t＝4500s)-I(t＝0s)/mA | ????98 | ????148 | ????165 |
| ?I(t＝4500s)-I(t＝0s)/I(t＝0s) | ????140％ | ????251％ | ????174％ |
Zinc electrode can produce the dendrite phenomenon in charging process, dendritic growth can puncture barrier film and cause battery short circuit to lose efficacy.Therefore dendrite is that influence is an important factor of the service life of secondary cell of negative pole with zinc.Foamed brass has minimum current increases rate as can be seen from Table 2, and promptly the zinc deposition is the most uniform on the foamed brass, and dendritic growth is minimum.The zinc electrode that this explanation is collector (matrix) with the foamed brass can effectively suppress the growth of zinc dendrite.
Embodiment 4
To be collector (matrix) by embodiment 1 prepared foamed brass, make comparisons, carry out volume test with collector (matrix) nickel foam that secondary cell is commonly used.With 52wt.%Zn powder, 36wt.%ZnO, 10wt.% graphite, 2wt.%Ca (OH)
2Or zincic acid calcium altogether 1g fully mix with mortar, add 1 PTFE, 2 absolute ethyl alcohols and an amount of saturated limewater are mixed well, and are coated in 1 * 1cm respectively
2Nickel foam and foamed brass on, compressing tablet is as negative pole.The anodal large tracts of land Ni (OH) that adopts
2Electrode.Reference electrode adopts the HgO/Hg electrode.Barrier film adopts glassine paper and the double-deck barrier film of nonwoven fabrics.0.05C charge 30 hours, left standstill 20 minutes, 0.1C is discharged to-0.85V (vs.HgO/Hg), leaves standstill 20 minutes.By above step reciprocation cycle.Discharge capacity～cyclic curve is seen Fig. 3, and wherein a is nickel foam collector (matrix), and b is foamed brass collector (matrix).By among Fig. 3 as can be seen, the b electrode just reaches very high capacity in former weeks.The a electrode is more or less the same at preceding 10 all capacity and b electrode, but in 13 just decay rapidly of week back capacity.And the b electrode has kept higher relatively capacity always in the circulation in whole 40 weeks, and promptly cycle life is higher.Thus, be that the zinc negative pole of collector (matrix) has higher discharge capacity and cycle life with the foamed brass, foamed brass is a kind of outstanding zinc-nickel cell collector (matrix).
Claims (6)
1, a kind of is the foam-metal current collector body of the secondary cell of negative pole with zinc, it is characterized in that it is to have foamed space structure, interconnective metallic framework constitutes three-dimensional space network structure, surface composition is weight cupric 68%～75% and the ormolu that contains zinc 32～25%, i.e. foamy brass.
2, described according to claim 1 is the foam-metal current collector body of the secondary cell of negative pole with zinc, and the thickness that it is characterized in that described foamy brass is 0.01 μ m～1000 μ m.
3, claim 1 is described is the preparation method of foam-metal current collector body of the secondary cell of negative pole with zinc, it is characterized in that it comprises the steps:
(1), be that the foamed sheet of 0.1mm～10mm is through overactivation, sensitization, at Cu salt/EDTA/ methyl alcohol/NiCl with thickness 1)
2Solution system in, be reducing agent with formaldehyde or inferior sodium phosphate, carry out electroless copper, the pH value of solution value is 7～14, reaction temperature is 20～80 ℃, the reaction time is 0.3～10 hour;
2) will carry out the foamed plastics of electroless copper, in resistance furnace, carry out high-temperature process, during processing with Ar, N
2, H
2One or more gaseous mixtures in the gas are protected, and treatment temperature is 200～1000 ℃, and the processing time is 0.3～10 hour, obtains foam copper after the processing;
3) foam copper is electroplated layer of copper, thereby play ruggedized construction, the effect of surface evening;
4) with foam copper brass plating in the tank liquor system of Cu salt/Zn salt/potassium pyrophosphate/glycerine/oxalic acid/dipotassium hydrogen phosphate, anode is brass or copper coin+zine plate or inert metal, and cathode-current density is 0.01～10A/dm
2, the pH value of solution value is 7～14, and electroplating temperature is 20～80 ℃, and electroplating time is 1～120 minute, obtains foamed brass after the plating;
Or (two), will be by in (one) 2) or 3) the resulting foam copper of step, electroplate layer of copper earlier, after ethylenediamine solution was handled, re-plating one deck zinc carried out high-temperature process then, during processing with Ar, N
2, H
2One or more gaseous mixtures in the gas are protected, and treatment temperature is 200～1000 ℃, and the processing time is 0.3～10 hour; Also obtain foamed brass after the processing;
Or (three), at other foam metal matrix, as nickel foam, foamed aluminium, foam lead, foam silver, according in (one) 4) or two) method handle, also can obtain foamed brass.
4, described according to claim 3 is the preparation method of foam-metal current collector body of the secondary cell of negative pole with zinc, it is characterized in that it comprises the steps:
To carry out annealing in process or surface treatment by (one) or (two) or (three) resulting foamed brass, Ar, N during annealing
2, H
2One or more gaseous mixtures in the gas are protected, and annealing temperature is 200～1000 ℃, and annealing time is 0.3～100 hour, and surface treatment comprises that chemistry or electrochemical polish, element replace.
5, described according to claim 3 is the preparation method of foam-metal current collector body of the secondary cell of negative pole with zinc, it is characterized in that described tank liquor system can be cyanide salt, cyanide salt+pyrophosphate, HEDP, ethylenediamine, carbonate, rhodanate, sulfate, oxalates, tartaric acid, triethanolamine, thiosulfate, chlorate+thiosulfate, ferrocyanide or the formamide tank liquor system that contains the glycerine additive.
6, claim 1 is described is the application of foam-metal current collector body of the secondary cell of negative pole with zinc, it is characterized in that also can being used for other alkaline secondary cell, comprises Ni-MH battery, nickel-cadmium cell or nickel iron cell, does collector (matrix).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021004080A CN1172388C (en) | 2002-01-24 | 2002-01-24 | Foam-metal current collector of secondary battery using zinc as negative electrode and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021004080A CN1172388C (en) | 2002-01-24 | 2002-01-24 | Foam-metal current collector of secondary battery using zinc as negative electrode and its preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1360356A true CN1360356A (en) | 2002-07-24 |
| CN1172388C CN1172388C (en) | 2004-10-20 |
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|---|---|---|---|
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| WO2007076650A1 (en) * | 2005-12-31 | 2007-07-12 | 72G Group Limited | Sintered hollow polyurethane spongy metal structure and preparation method thereof |
| CN101202357B (en) * | 2006-12-15 | 2010-05-12 | 中国电子科技集团公司第十八研究所 | Cylinder type zinc-nickel storage battery |
| CN102263269A (en) * | 2011-06-22 | 2011-11-30 | 广东博特动力能源有限公司 | Cathode active material, inclined pull-net cathode matrix and cathode of nickel-zinc batteries and preparation method of cathode |
| CN102437313A (en) * | 2011-12-08 | 2012-05-02 | 中国电子科技集团公司第十八研究所 | Negative electrode for high-power metal lithium battery |
| CN103924274A (en) * | 2013-01-10 | 2014-07-16 | 中国科学院上海微***与信息技术研究所 | Method for enhancing antioxidation capacity of foam copper |
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| CN103924274A (en) * | 2013-01-10 | 2014-07-16 | 中国科学院上海微***与信息技术研究所 | Method for enhancing antioxidation capacity of foam copper |
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| CN111755757B (en) * | 2019-03-26 | 2023-12-15 | 丰田自动车株式会社 | Method for manufacturing nickel-zinc battery |
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| CN112216809B (en) * | 2019-07-11 | 2022-03-18 | 深圳市比亚迪锂电池有限公司 | Metal cathode, preparation method thereof and lithium ion battery |
| CN111769251A (en) * | 2020-04-10 | 2020-10-13 | 上海大学 | Method for protecting metal electrode |
| CN112290007A (en) * | 2020-10-27 | 2021-01-29 | 燕山大学 | Preparation method of zinc-copper alloy cathode with self-supporting structure |
| CN113066990A (en) * | 2021-04-25 | 2021-07-02 | 中南大学 | Preparation method and application of zinc negative electrode modified three-dimensional current collector |
| CN113066990B (en) * | 2021-04-25 | 2022-09-16 | 中南大学 | Preparation method and application of zinc negative electrode modified three-dimensional current collector |
| CN116936815A (en) * | 2023-09-18 | 2023-10-24 | 宁德时代新能源科技股份有限公司 | Negative current collector, preparation method thereof, negative electrode plate, lithium metal battery and power utilization device |
| CN116936815B (en) * | 2023-09-18 | 2024-02-27 | 宁德时代新能源科技股份有限公司 | Negative current collector, preparation method thereof, negative electrode plate, lithium metal battery and power utilization device |
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