CN106257714A - A kind of new system lithium ion battery and preparation method thereof - Google Patents
A kind of new system lithium ion battery and preparation method thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses a kind of new type lithium ion battery and preparation method thereof.This lithium ion battery comprises positive pole, negative pole, the 3rd electrode, electrolyte and barrier film, 3rd electrode is lithium metal or lithium intercalation compound and adhesive, conductive agent and auxiliary functionality become the combination electrode being grouped into, and the 3rd electrode current collecting body is LITHIUM BATTERY nickel plating rustless steel, rustless steel, nickel, aluminum.3rd electrode production process is that mentioned component lithium paper tinsel, water paste or the oil system slurry made are in metal battery case inner surface riveted or coating, bonding, drying and forming-film process.The lithium ion battery that the present invention provides has the circulation of equal system common batteries more than three times, storage life, and capacity and is at least above equal system common batteries capacity 5～20%.Simultaneously by the data monitoring of the 3rd electrode, can be as the effective ways quickly judging battery plus-negative plate decay.
Description
Technical field
The present invention relates to technical field of lithium ion, have particularly to oneNovelSelfreparing and battery from control function.
Background technology
Along with the gradually aggravation that people's environmental consciousness strengthens and oil is day by day exhausted, there is electric automobile energy-efficient, zero-emission advantage and receive much attention.Lithium ion battery as new-energy automobile core technology generally there is cycle life and calendar life is too short, and efficiency is on the low side first, and inside battery situation is difficult to the problems such as monitoring, has had a strong impact on the technological progress of new-energy automobile.The major reason causing these problems is activity Li+Loss and lack reference electrode monitoring.In order to extend the service life of battery, inside battery situation of change during monitoring uses simultaneously, the present invention on the basis of normal two electrode system lithium electricity, increases the 3rd electrode that can supplement lithium, solves the problems referred to above.
Summary of the invention
Technical problem solved by the invention is to provide three-electrode system lithium ion battery, use the 3rd electrode as lithium ion supplementary source and reference electrode, in order to solve service life and detection vacancy defect present in above-mentioned technical background.
Technical problem solved by the invention realizes by the following technical solutions:
A kind of combination electrode of preparation is as the 3rd electrode, so that when battery uses capacity to drop to a certain degree, battery system is carried out lithium source supplement, simultaneously by gathering positive pole vs the 3rd electrode, the open circuit voltage variations of negative pole vs the 3rd electrode, judge cell decay situation, in order to battery management system makes the feedback of correspondence.
This battery system the 3rd electrode composition is mainly become, by lithium metal or lithium intercalation compound and adhesive, conductive agent and auxiliary functionality, the combination electrode being grouped into, lithium metal or lithium intercalation compound accounting prioritizing selection 90～100%, conductive agent accounting prioritizing selection 0.5～5%, adhesive prioritizing selection 2～5%.
3rd electrode comprises lithium intercalation compound selected from lithium transition-metal oxide and polyanion positive electrode, it is selected from cobalt acid lithium and complex, LiFePO4 and complex thereof, LiMn2O4 and complex thereof, tertiary cathode material and complex thereof, rich lithium material and complex thereof.
3rd electrode package is chosen as conductive black containing conductive agent, acetylene black, vapor-phase thermal cracking Carbon fibe, CNT, electrically conductive graphite, one or several the combination in Graphene.
3rd electrode package is chosen as Kynoar containing adhesive, polyacrylate, butadiene-styrene rubber class, the combination of one or more in polyurethanes.
The M of the certain mass of the 3rd electrode component1Lithium metal or lithium intercalation compound, if metal Li, its mass M1Calculate: 0*CBattery reversible capacity(Ah)/3.82936～1CBattery reversible capacity(Ah)/3.82936g, wherein weight prioritizing selection 0.2CBattery reversible capacity(Ah)/3.82936g；If lithium intercalation compound, its weight M1Calculate: 0*CBattery reversible capacity(Ah)/CGram volume～50CBattery reversible capacity(Ah)/CGram volume,.(CGram volume: the capacity that unit mass lithium intercalation compound can play).
The preparation process of the 3rd electrode is divided into two kinds of forms, the first, use the mode of slurry coating battery container inner surface；The second uses the mode of metal Li paper tinsel riveted metal shell inner surface.The slurry that first kind of way uses, preparation process is as follows, takes a certain amount of lithium intercalation compound, conductive agent, adhesive, uses specific solvent (NMP/H2O/ ethanol), it is sufficiently stirred for, after being uniformly dispersed, is coated on metal shell inner surface, application place is illustratedFigureSeeFigure 3, it is coated with preferential position 3.The second way, metal Li paper tinsel riveting process need for environment is carried out at 99.99% ar gas environment, and riveting location is shown in signalFigure 3, rivet preferential position 3.
For promoting the purpose of capacity of lithium ion battery in the present invention, fluid injection terminates rear battery core, after abundant moistening, to form charge circuit between the 3rd electrode and negative pole, is charged, and charging current is I, and the charging interval is T.I=(0～100) * CRated capacity, T=CRated capacity/ I, charging current limited employing 0.001CRated capacity。
For the purpose extending lithium ion battery service life in the present invention, after battery uses or stores a period of time, with 0～10C10A carries out capacity demarcation to battery, preferentially with 0.5C10A current versus cell capacity is demarcated, counting loss capacity, derives the quantity in supplementary lithium source.
Detailed process is as follows:
1) with 0～10C10A demarcates real-time battery capacity C1；
2) this crowd of battery average amount constant volume C is knownBattery reversible capacity；
3) determine that battery loses capacity C2=CBattery reversible capacity-C1；
4) battery is with 0～10C10Battery is charged by A, and charge cutoff voltage is 0～10V；
5) using electronic load to connect negative pole and the 3rd electrode composition battery, discharge with electric current I, cut-off condition is to reach t (h) discharge time, or reaches discharge cut-off voltage lower limit, electric discharge lower limit by positive electrode and；
Determine that benefit Li electric current density is I=Ia* S, wherein Ia: 0～20000mA/cm2, S:Li sheet metal or the long-pending (cm of lithium intercalation compound film coated surface2)；Supplement Li charging interval t:0～1000*C2/Ia, preferential employing 0.90 C2/Ia；
Further, use the purpose of process condition for the present invention monitors battery, during lithium ion battery uses and stores, gather the attenuation data of anode negative material.This process mainly judges the respective attenuation of anode, negative pole by positive pole VS the 3rd electrode, the platform voltage of negative pole VS the 3rd electrode, the situation of change of open-circuit voltage (@X SOC).
Detailed process is as follows:
1), after battery partial volume terminates, gather positive pole VS. the 3rd electrode, negative pole VS. the 3rd electrode discharge curve, full battery discharge curve respectively, calculate mean voltage, computational methods: discharge energy/discharge capacity, be designated as V respectivelyave1、Vave2、Vave3；
2) battery battery capacity decay after circulation or storage, now, then gathers positive pole VS. the 3rd electrode, and negative pole VS. the 3rd electrode discharge curve calculates mean voltage, computational methods: discharge energy/discharge capacity, is designated as V respectivelyave11、Vave12、Vave13；
3) positive pole decay weight is calculated: x1=(Vave1-Vave11)/(Vave3-Vave13), negative pole decay weight: x1=(Vave2-Vave12)/(Vave3-Vave13)
By comparing the size of x1, x2, it is judged that the respective situation of change of both positive and negative polarity during cell decay.
This lithium ion battery, compared with traditional lithium ion battery, has the advantages that
The lithium ion battery that the present invention provides has the circulation of equal system common batteries more than three times, storage life, and capacity and is at least above equal system common batteries capacity 5～20%.Simultaneously by the data monitoring of the 3rd electrode, can quickly judge battery plus-negative plate attenuation, it is simple to battery management system makes feedback in time.
Accompanying drawing illustrates:
Figure 1It is that positive pole, negative pole, the 3rd electrode, housing are relative to position；
Figure 2It it is the zigzag lamination assembling structure of positive pole, negative pole, barrier film；
Figure 3It it is chemical conversion/capacity reparation signalFigure；
Figure 4It isNovelNumber battery capacity repair before and after discharge curve；
Figure 5It isNovelNumber battery 4WEEK store before and after different phase discharge curve；
It is embodied as:
For the technological means making the present invention realize, creation characteristic, reach purpose and be easy to understand with effect, below in conjunction with instantiation, the present invention is expanded on further.
SeeFigure 1~Figure 2, a kind of based on LiFePO 4 material/Delanium system li-ion systemsNovelLithium-ion battery system, the 3rd electrode uses metal shell as collector.
Figure 1In mark 1 be the LiFePO 4 material/Delanium laminated cell assembled, mark 1 cross-sectional structureSuch as figure 2Shown in, positive pole/barrier film/negative pole uses zigzag lamination to assemble, and mark 2 is the position of the 3rd electrode, and mark 3 is battery core Positive Poles, and mark 4 is battery core negative pole pole.
Figure 2Middle mark 1 is PP/PE barrier film, and mark 2 is cathode pole piece, and negative current collector is 10um Copper Foil, and mark 3 is anode pole piece, and negative current collector is 15um aluminium foil.
Figure 3For battery in formation process and the signal of battery repair processFigure, mark 1 is battery core body, and mark 2 is the 3rd electrode, and mark 3 is Positive Poles, and mark 4 is negative pole pole, and mark 5 is electronic load.The first situation, when battery is in the chemical conversion stage, forms loop between negative pole pole and the 3rd electrode, the 3rd electrode is anode, and negative pole is negative electrode, and external charge power supply is charged, and is melted into battery cathode；The second situation, battery repair process, anode negative pole assembles discharge loop in advance, is discharged to by voltage, and then, positive pole and the 3rd electrode composition discharge loop, external connected electronic loads, and the time discharges according to the rules, repairs battery.
In the present embodiment, positive pole, cathode pole piece use the automobile-used electrodes of lithium-ion batteries of LiFePO 4 material of 26Ah, the 3rd electrode to use lithium titanate to be lithium intercalation compound, and the 3rd electrode uses the mode of compound film electrode to be prepared.
Positive pole adhesive uses Kynoar, and conductive agent uses conductive black and SWCN.The accounting of LiFePO4 is 94%, and the accounting of Kynoar is 3%, and the ratio of conductive agent white carbon black is 2%, and the ratio of SWCN is 1%, and the solvent that preparation process uses is NMP.The slurry viscosity of preparation is 3500CP (Bo Le flies DV-2, No. 4 rotors), uses squash type coating method to be coated at aluminium foil surface.
Negative pole adhesive uses Kynoar, and conductive agent uses conductive black.The accounting of Delanium is 94%, and the accounting of Kynoar is 4%, and the ratio of conductive agent white carbon black is 2%, and the solvent that preparation process uses is NMP.The slurry viscosity of preparation is 4000CP (Bo Le flies DV-2, No. 4 rotors), uses squash type coating method to be coated on Copper Foil paper tinsel surface.
3rd electrode adhesive uses Kynoar, and conductive agent uses conductive black.Wherein the accounting of the lithium intercalation compound lithium titanate of the 3rd electrode is 90%, and the accounting of Kynoar is 6%, and the ratio of conductive agent white carbon black is 4%, and the solvent that the 3rd electrode production process uses is NMP.The slurry viscosity of preparation is 1000CP (Bo Le flies DV-2, No. 4 rotors), solids content 38%, and aluminum hull housing bottom is coated by the mode using dosing pump to inject.
Slurry coated weight is calculated as follows:
Lithium intercalation compound weight M1=26000*0.3/CGram volume=26000*0.2mAh/165mAh/g=32.0g；
Slurry coat weight M=32/0.9/38%=92.1g.
After slurry injects aluminum casing bottom, housing is positioned in 100 DEG C of drying baker and is dried, dry environment dew point-40 DEG C.It is standby that aluminum hull housing after dry end is placed on 25 DEG C of environment of relative humidity-10%@.
In the present embodiment,NovelSystem battery core capacity gets a promotion.Capacity boost process is that the LiFePO4/Delanium battery core fluid injection of normal system terminates, abundant moistening, to form charge circuit between the 3rd electrode and negative pole, is charged, and charging current is 26mA, and the charging interval is 10h.
Battery carries out continuous chemical conversion and partial volume according to normal flow, and compared with batch common batteries, and capacity boost 8%～9%.AsFollowing table 1Shown in.
Table 1 NovelBattery core capacity boost data arrangeTable
The present invention extends lithium ion battery method in service life,NovelBattery, at 55 DEG C of environment, does calendar life test.After 4 week, high temperature was shelved, with 0.5C10A carries out capacity demarcation to battery, now relative to initial capacity capability retention 81.3%.According to the method in the present invention, according to loss capacity, derive the quantity in supplementary lithium source, calculate process as follows:
Calculate and supplement lithium source capacity:
C=90%* (CBattery reversible capacity-CResidual capacity)=0.9*0.187*26000=4376mAh
Battery core positive pole and negative pole composition loop, be discharged to blanking voltage 3.0V, vacate positive pole embedding lithium room, form loop with positive pole and the 3rd electrode, positive pole is carried out lithium source and supplements, and supplemental current 52mA, the time is 84h.With 0.5C after end10A carries out capacity demarcation to battery, capacity resuming to 92.3%, full battery discharge and positive pole vs the 3rd electrode, negative pole vs the 3rd electrode discharge curveSuch as figure 4Shown in.After battery capacity is supplemented,NovelThe battery storage life-span compares data with common size battery and seesTable 2。
Table 2 NovelNumber battery cycle life
NovelBattery core, during storing, by the 3rd electrode, timing acquiring positive pole VS the 3rd electrode, the platform voltage situation of change between negative pole vs the 3rd electrode, judges battery core both positive and negative polarity voltage platform situation of change during storing with this, gathers dataSuch as figure 5Shown in.Monitoring decision method according to aforesaid voltage, during storage, anode voltage platform does not changes significantly, and the decline of cathode voltage platform is the main cause that cell voltage platform declines.Reference both positive and negative polarity discharge curve is by the difference of current potential, thus it is speculated that being that activity Li loses at negative pole, cause the embedding Li of positive pole not enough, now battery management system should process this information, uses the 3rd electrode to battery supplementary loss Li source.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.Skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; the principle that the present invention is simply described described in above-described embodiment and description; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements both fall within scope of the claimed invention.Claimed scope is defined by appending claims and equivalent thereof.
Claims (23)
1. a new type lithium ion battery, including can the positive pole of reversible embedding de-lithium, negative pole, electrolyte, barrier film, shell, it is characterised in that include the 3rd electrode that can supplement loss lithium ion.
2. the 3rd electrode described in claim 1, it is characterised in that: in the chemical conversion stage, the 3rd electrode and negative pole composition battery charge circuit, anticathode material carries out pre-chemical conversion, when positive pole is not involved in formation process, completes negative terminal surface SEI film forming procedure；Meanwhile, during battery uses, loss activity Li in battery can be supplemented by the 3rd electrode as supplementing Li source.The auxiliary function of the 3rd electrode is the attenuation data gathering anode negative material.
Lithium ion battery the most according to claim 1, its housing form is square aluminum hull, square box hat, square plastic shell and cylindrical steel, cylindrical aluminum hull.The length range of all material rectangular cell: 0～1000mm, width range 0～1000mm, thickness range: 0～1000mm.The cylindrical battery of all material, diameter range: 0～1000mm, altitude range: 0～1000mm.
Lithium ion battery the most according to claim 1, it is characterised in that: the 3rd electrode package is containing component: certain mass M1Lithium metal membrane or lithium intercalation compound composite membrane (if lithium intercalation compound film, containing certain mass M in the 3rd electrode2Conductive agent, certain mass M3Adhesive) its structure is as shown in Figure 1.
Lithium ion battery the most according to claim 1, the 3rd electrode is lithium intercalation compound, containing certain mass M in the 3rd electrode2Conductive agent, certain mass M3Adhesive.Wherein M2Accounting for whole lithium intercalation compound electrode proportion is: 0～100%, M3Accounting for whole lithium intercalation compound electrode proportion is: 0～100%.
3rd electrode the most according to claim 4, its feature is being selected from one or more in lithium transition-metal oxide or polyanion positive electrode with lithium intercalation compound, preferably cobalt acid lithium and complex thereof, LiFePO4 and complex thereof, LiMn2O4 and complex thereof, tertiary cathode material and complex thereof, the one or more combination in rich lithium material and complex thereof.
Certain mass M the most according to claim 32Conductive agent, conductive agent is chosen as conductive black, acetylene black, vapor-phase thermal cracking Carbon fibe, CNT, electrically conductive graphite, one or several the combination in Graphene.
Certain mass M the most according to claim 33Adhesive, adhesive is chosen as Kynoar, polyacrylate, butadiene-styrene rubber class, the combination of one or more in polyurethanes.
Lithium ion battery the most according to claim 1, it is characterised in that the installation site of its 3rd electrode, for six inner surfacies of rectangular cell, or cylindrical battery inner surface, bottom or top, its position is as shown in Figure 2.
Lithium ion battery the most according to claim 1, its assembling mode is as follows, positive pole/barrier film/negative pole, assembles according to zigzag or winding, and the 3rd electrode is attached to battery metal shell inner surface by coating and riveting method and forms membrane electrode.The preparation process of both positive and negative polarity lithium intercalation compound film includes: lithium intercalation compound/conductive agent/adhesive is sufficiently mixed dispersion in specific solvent, and formation is uniformly distributed, finely disseminated uniform sizing material, carries out even spread according to specific coating carrying capacity at copper aluminium foil surface.
11. preparation method of lithium ion battery according to claim 1, it is characterized in that the preparation process of the 3rd electrode lithium intercalation compound film includes: the 3rd electrode is lithium intercalation compound, conductive agent, the composite membrane of adhesive formation, its preparation process is as follows, lithium intercalation compound/conductive agent/adhesive is sufficiently mixed dispersion in specific solvent, formation is uniformly distributed, finely disseminated even phase slurry, slurry quantitatively injects housing by dosing pump and specifies position, the most standby.
12. preparation method of lithium ion battery according to claim 10, it is characterised in that the specific solvent that lithium intercalation compound combination electrode preparation process uses is selected from H2Ketone or one or several the combinations of alcohols low molecular weight solvent such as O or NMP, acetone, ethanol.
13. preparation method of lithium ion battery according to claim 10, it is characterised in that: the 3rd electrode component contains the M of certain mass1Lithium metal or lithium intercalation compound, its mass M1For: 0*CBattery reversible capacity(Ah)/3.82936～50CBattery reversible capacity(Ah)/3.82936；If lithium intercalation compound, its weight M1Calculate: 0*CBattery reversible capacity(Ah)/CGram volume～50CBattery reversible capacity(Ah)/CGram volume。(CGram volume: the capacity that unit mass lithium intercalation compound can play).
14. the 3rd electrodes according to claim 1, it is characterised in that lithium intercalation compound slurry, coating, the mode of drying and forming-film or the mode with battery container inner surface riveted are prepared in the connected mode employing between the 3rd electrode and shell.
15. the 3rd electrodes according to claim 1, promote battery capacity 5-20% in the following manner, and fluid injection terminates rear battery core, after abundant moistening, to form charge circuit between the 3rd electrode and negative pole, are charged, and charging current is I, and the charging interval is T.I=(0～100) * CRated capacity, T=CRated capacity/I。
16. the 3rd electrodes according to claim 1, it is characterised in that can supplement lithium ion timely in the case of losing by lithium ion in the battery, mode and the step of its supplementary lithium ion are as follows:
1) circulating battery n time or store after n days；(n:0～100000)
2) with 0～10C10A demarcates real-time battery capacity C1；
3) this crowd of battery average amount constant volume C is knownBattery reversible capacity；
4) determine that battery loses capacity C2=CBattery reversible capacity-C1；
5) battery is with 0～10C10Battery is charged by A, and charge cutoff voltage is 0～10V；
6) using electronic load to connect negative pole and the 3rd electrode composition battery, discharge with electric current I, discharge time is t (h)；
7) determine that benefit Li electric current density is I=Ia* S, wherein Ia: 0～20000mA/cm2, S:Li sheet metal or the long-pending (cm of lithium intercalation compound film coated surface2)；Supplement Li charging interval t:0～1000*C2/Ia。
17. lithium ion batteries according to claim 1, it is characterised in that the auxiliary function of the 3rd electrode is the attenuation data gathering anode negative material, and it is as follows that it realizes process:
1), after battery partial volume terminates, gather positive pole VS. the 3rd electrode, negative pole VS. the 3rd electrode discharge curve, full battery discharge curve respectively, calculate mean voltage, computational methods: discharge energy/discharge capacity, be designated as V respectivelyave1、Vave2、Vave3；
2) battery battery capacity decay after circulation or storage, now, then gathers positive pole VS. the 3rd electrode, and negative pole VS. the 3rd electrode discharge curve calculates mean voltage, computational methods: discharge energy/discharge capacity, is designated as V respectivelyave11、Vave12、Vave13；
3) positive pole decay weight is calculated: x1=(Vave1-Vave11)/(Vave3-Vave13), negative pole decay weight: x1=(Vave2-Vave12)/(Vave3-Vave13)
4) by comparing the size of x1, x2, it is judged that the respective situation of change of both positive and negative polarity during cell decay.
18. lithium ion batteries according to claim 1, it is characterized in that: positive electrode is lithium intercalation compound, selected from lithium transition-metal oxide or polyanion positive electrode, preferably cobalt acid lithium and complex thereof, LiFePO4 and complex thereof, LiMn2O4 and complex thereof, tertiary cathode material and complex thereof, one or several in rich lithium material and complex thereof.
19. lithium ion batteries according to claim 1, it is characterised in that: electrolyte is selected from liquid electrolyte.Wherein, described liquid electrolyte includes the electrolyte based on protic organic solvent and ionic liquid.
Electrolyte based on protic organic solvent is at least selected from ether electrolyte and carbonic ester electrolyte.The solvent of carbonic ester electrolyte in dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethylene carbonate and Allyl carbonate at least one or several, solute in lithium hexafluoro phosphate, sodium perchlorate, lithium iodide and two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) at least one or several；The solvent of ether electrolyte is selected from 1, in 3-dioxolanes, glycol dimethyl ether and TRIGLYME at least one or several, solute in lithium hexafluoro phosphate, lithium perchlorate, lithium iodide and two (trimethyl fluoride sulfonyl) imine lithium at least one or several.
20. lithium ion batteries according to claim 1, it is characterised in that: material is the compound of one or more in graphite, amorphous carbon, carbonaceous mesophase spherules, silica-base material, transition metal oxide, metal Li.
21. lithium ion batteries according to claim 1, it is characterised in that: barrier film is the one that polypropylene, polyethylene, polypropylene, polyethylene, polypropylene, polyethylene/polypropylene material ion guide are led in film.
22. 1 kinds of energy storage elements, it is characterised in that: containing the lithium ion battery described in claim 1.
23. 1 kinds of portable electric appts, it is characterised in that: use the energy storage elements described in claim 20.
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| CN111244458A (en) * | 2020-01-19 | 2020-06-05 | 中国科学院电工研究所 | Pre-lithiation electrode |
| CN111584938A (en) * | 2020-04-30 | 2020-08-25 | 汉腾新能源汽车科技有限公司 | Lithium ion battery anode lithium supplementing method |
| CN115036465A (en) * | 2021-03-04 | 2022-09-09 | 上海卡耐新能源有限公司 | Lithium metal negative electrode, preparation method thereof and lithium secondary battery |
| CN113113558A (en) * | 2021-03-22 | 2021-07-13 | 大连中比动力电池有限公司 | Three-electrode system of lithium ion battery and preparation method thereof |
| CN113113558B (en) * | 2021-03-22 | 2022-04-26 | 大连中比动力电池有限公司 | Three-electrode system of lithium ion battery and preparation method thereof |
| CN113078367A (en) * | 2021-03-29 | 2021-07-06 | 中南大学 | Manufacturing method of high-energy-density flexible package lithium ion battery |
| CN113078367B (en) * | 2021-03-29 | 2023-10-20 | 中南大学 | Manufacturing method of high-energy-density flexible package lithium ion battery |
| CN116598418A (en) * | 2023-05-22 | 2023-08-15 | 皖西学院 | Three-electrode battery and pre-lithiation pre-lithium amount calculating method thereof |
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