CN111524713B - Cylindrical lithium ion capacitor and preparation method thereof - Google Patents

Cylindrical lithium ion capacitor and preparation method thereof Download PDF

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CN111524713B
CN111524713B CN202010326016.7A CN202010326016A CN111524713B CN 111524713 B CN111524713 B CN 111524713B CN 202010326016 A CN202010326016 A CN 202010326016A CN 111524713 B CN111524713 B CN 111524713B
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lithium
negative
capacitor
positive
foil layer
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CN111524713A (en
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李晶
赵丹
赵晓东
唐曼琴
郭建强
唐鑫
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Sichuan Province Science City Jiuxin Science & Technology Co ltd
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Southwest University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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
    • Y02E60/13—Energy storage using capacitors

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  • Chemical & Material Sciences (AREA)
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Abstract

The invention relates to the technical field of electrochemical energy storage devices, and discloses a cylindrical lithium ion capacitor, which comprises a cylindrical and hollow capacitor shell, and a composite lithium source, a first diaphragm and a winding core which are sequentially arranged in the inner cavity of the capacitor shell from bottom to top; the composite lithium source comprises a foamed nickel layer and a metal lithium layer; the winding core is formed by winding a positive plate, a second diaphragm and a negative plate which are arranged at intervals; the positive plate comprises an aluminum foil layer, a positive active material and a positive tab, wherein the positive active material is uniformly coated on the outer surface of the aluminum foil layer, and the positive tab is positioned at the upper end of the aluminum foil layer; the negative plate comprises a copper foil layer, a negative active material and a negative tab, wherein the negative active material is uniformly coated on the outer surface of the copper foil layer, and the negative tab is positioned at the upper end of the copper foil layer; the invention also discloses a preparation method of the capacitor, which achieves the effects of improving the cycle performance and the capacity, shortening the preparation period and reducing the production cost, the equipment requirement and the manufacturing process difficulty.

Description

Cylindrical lithium ion capacitor and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemical energy storage devices, in particular to a cylindrical lithium ion capacitor and a preparation method thereof.
Background
The lithium ion capacitor has the characteristics of high energy density of the lithium ion battery and long service life and high power of the super capacitor, so that the lithium ion capacitor has wide market application prospect in the fields of Uninterruptible Power Supplies (UPS), instant compensation devices, electric vehicles, hybrid electric vehicles and the like. Currently, the core process for manufacturing lithium ion capacitors is in the negative electrode "pre-intercalation of lithium".
The current common methods for manufacturing lithium ion capacitors are as follows:
1. according to patent CN200580004509.2 of fuji heavy industry, perforated aluminum foil or copper foil is used as the positive and negative electrode foils, and lithium is used as a lithium source, and lithium is inserted into the negative electrode by short-circuiting the lithium metal with the negative electrode. However, the method of pre-embedding lithium has the problems that the price of the perforated copper foil and the perforated aluminum foil is high, the manufacturing process using the perforated pole piece is complex, the requirement on equipment is high, the period is as long as 10-15 days, and the like.
2. According to the report of Zhengjiaping article, passivated metal lithium powder (SLMP) is used as a lithium source, and is mixed with hard carbon by a dry mixing mode to prepare a negative electrode, and meanwhile, active carbon is used as a positive electrode to assemble a lithium ion capacitor monomer. However, the passivated lithium powder is expensive, and when lithium metal is intercalated into a carbon material on the negative electrode, voids are generated in the electrode, thereby causing problems such as a decrease in conductivity and a drop in active material.
3. According to the disclosure of Chinese patent document CN201810524433.5, a high irreversible capacity lithium-rich metal oxide (Li) is used2NiO2、Li2MoO3、Li5FeO4Etc.) is mixed with activated carbon to prepare a positive electrode, one of hard carbon, soft carbon and graphite is taken as a negative electrode, and the lithium ion capacitor is assembled. However, the addition amount of the lithium-rich metal oxide with high irreversible capacity accounts for 10-40% of the total mass of the positive electrode, so that the mass ratio of the activated carbon is low, and the energy density of the lithium ion capacitor is influenced.
In view of the foregoing, there is a need for a lithium ion capacitor and a method for manufacturing the same, which can improve cycle performance and capacity, shorten manufacturing cycle, and reduce production cost, equipment requirements, and manufacturing process difficulty.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a cylindrical lithium ion capacitor and a preparation method thereof, so as to at least achieve the effects of improving the cycle performance and the capacity, shortening the preparation period and reducing the production cost, equipment requirements and manufacturing process difficulty.
The purpose of the invention is realized by the following technical scheme: a cylindrical lithium ion capacitor comprises a cylindrical and hollow capacitor shell, and a composite lithium source, a first diaphragm and a winding core which are sequentially arranged in an inner cavity of the capacitor shell from bottom to top;
the composite lithium source comprises a nickel foam layer and a metal lithium layer, and the nickel foam layer is connected with the bottom of the capacitor shell; the winding core is formed by winding a positive plate, a second diaphragm and a negative plate which are arranged at intervals, and a rubber plug is arranged at the upper end of the winding core;
the positive plate comprises an aluminum foil layer, a positive active material and a positive tab, wherein the positive active material is uniformly coated on the outer surface of the aluminum foil layer, and the positive tab is positioned at the upper end of the aluminum foil layer;
the negative plate comprises a copper foil layer, a negative active material and a negative electrode tab, wherein the negative active material is uniformly coated on the outer surface of the copper foil layer, and the negative electrode tab is positioned at the upper end of the copper foil layer.
According to the technical scheme, the composite lithium source is arranged at the bottom of the inner cavity of the capacitor shell, so that lithium ions are directly diffused into the negative plate from bottom to top only under the action of an electric field force without perforating, and then are directly diffused to the negative electrode of the whole capacitor through the gaps among the first diaphragm, the positive plate and the negative plate, and the effects of avoiding using expensive perforated copper, aluminum foil and a complex coating process under the condition of ensuring the cycle performance and the capacity are achieved; meanwhile, a first diaphragm is added between the composite lithium source and the winding core, so that the effect of preventing the lithium source from being short-circuited with the positive electrode and the negative electrode is achieved.
Further, the width of the positive plate is 6-30 mm, and the width of the negative plate is 6-30 mm.
According to the technical scheme, the widths of the positive plate and the negative plate are limited, so that the path from the bottom to the top of lithium ions diffused is relatively reduced, the difficulty degree of lithium ion diffusion is reduced, the lithium pre-embedding of the negative electrode of the lithium ion capacitor is sufficient, the effective number of lithium ions is ensured, and the effects of improving the capacity and the cycle performance are achieved.
Further, the thickness of the first separator is 50 to 150 μm, preferably 100 μm.
Since the thicker the first membrane is, the better the isolation effect is, the lower the risk of contact; through the technical scheme, the thickness of the first diaphragm is limited, and the effect of reducing the production cost while ensuring the safety is achieved.
Further, the composite lithium source and the first diaphragm are both cylindrical, the diameter of the composite lithium source is equal to that of the winding core, and the diameter of the first diaphragm is equal to the inner diameter of the capacitor shell.
Further, the thickness P of the metal lithium layer is calculated from the first discharge capacity of the negative electrode, and the calculation formula is as follows:
p ═ total capacity of first discharge of negative electrode/capacity of lithium ×. lithium density ×. lithium source wafer area;
wherein the lithium capacity is 3860mAh/g, the lithium density is 0.534g/cm3, and the unit of the thickness P is cm.
Further, the positive active material comprises activated carbon, and the material of the positive electrode tab comprises aluminum; the negative active material includes one or more of graphite, hard carbon, and soft carbon, and the material of the negative tab includes copper.
Further, the material of the first diaphragm comprises at least one of polyethylene, polypropylene and cellulose, the material of the second diaphragm comprises one or more of polyethylene, polypropylene and cellulose, and the material of the capacitor shell comprises steel.
A preparation method of a cylindrical lithium ion capacitor comprises the following steps:
s1, winding the negative pole piece, the second diaphragm and the positive pole piece which are sequentially arranged at intervals to obtain a cylindrical battery cell, and then heating and drying to obtain a winding core;
s2, installing a rubber plug at the top of the winding core to obtain a winding core to be installed;
s3, welding a foamed nickel layer of the composite lithium source with the bottom of the capacitor shell, and sequentially placing the first diaphragm and the to-be-installed winding core to obtain a to-be-processed shell;
s4, injecting organic electrolyte into the to-be-treated shell, performing roller groove and sealing treatment, and standing at 40-50 ℃ for 24-48 h to obtain a to-be-treated capacitor; the step of high-temperature standing enables the organic electrolyte to better infiltrate the positive plate and the negative plate;
s5, pre-embedding lithium into the negative electrode of the capacitor to be processed in a constant current discharging mode by taking the negative electrode as a working electrode and a metal lithium electrode as an auxiliary electrode to obtain a pre-embedded lithium capacitor;
s6, the pre-embedded lithium capacitor is subjected to heating forming treatment to obtain the lithium ion capacitor.
Further, in S1, the method for preparing the positive electrode sheet includes the steps of:
s7, sequentially adding a thickening agent, a conductive agent, the positive active material and an adhesive in a mass ratio of 1.5:8:85:5.5 into water, wherein the stirring time is 1-3 hours after each material is added, and finally obtaining slurry I with the viscosity of 1000-3000 cP;
s8, uniformly coating the slurry I on the outer surface of the aluminum foil layer, and then drying and carrying out double-roller cutting treatment to obtain a pole piece I to be welded;
and S9, welding the positive electrode lug at the upper end of the pole piece I to be welded to obtain the electrode.
Further, in S1, the method for preparing the negative electrode sheet includes the following steps:
s10, sequentially adding a thickening agent, a conductive agent, the negative active material and a bonding agent into water in a mass ratio of 1.2:1.3:94:3.5, wherein the stirring time is 1-3 h after each material is added, and finally obtaining slurry II with the viscosity of 1000-3000 cP;
s11, uniformly coating the slurry II on the outer surface of the copper foil layer, and drying and cutting with a pair of rollers to obtain a pole piece II to be welded;
and S12, welding the negative pole lug at the upper end of the pole piece II to be welded to obtain the electrode.
Further, in S3, the preparation method of the composite lithium source is to perform composite rolling on the nickel foam and the lithium metal, and then perform die cutting treatment to obtain the composite lithium source.
Further, in S4, the organic electrolytic solution includes lithium hexafluorophosphate.
Further, in S5, the constant current is 0.01-0.05C, and the capacity of the pre-embedded lithium accounts for 75-90% of the first discharge capacity of the negative electrode.
Through the technical scheme, the current value of the constant current is limited, and the polarization between the composite lithium source and the negative electrode in the lithium pre-embedding process can be reduced, so that the lithium pre-embedding effect is ensured.
Meanwhile, when the pre-embedded lithium capacity is more than 90%, the negative electrode has the risk of lithium precipitation in the charge and discharge process of the lithium ion capacitor; when the pre-embedded lithium capacity is less than 75%, the voltage change of the negative electrode relative to the metal lithium is large in the charge-discharge process of the lithium ion capacitor, so that the quantity of lithium ions is insufficient, and the capacity exertion of the positive active carbon is influenced; therefore, the invention achieves the effect of ensuring the sufficient quantity of lithium ions and the capacity of the active carbon of the anode to play while reducing the risk of lithium precipitation by limiting the capacity of the pre-intercalated lithium.
The invention has the beneficial effects that:
1. according to the cylindrical lithium ion capacitor, the composite lithium source is arranged at the bottom of the inner cavity of the capacitor shell, so that lithium ions are directly diffused into the negative plate from bottom to top only under the action of an electric field force without perforating, and then are directly diffused into the negative electrode of the whole capacitor through the gaps among the first diaphragm, the positive plate and the negative plate, and the effects of avoiding using expensive perforated copper, aluminum foil and a complex coating process under the condition of ensuring the cycle performance and capacity are achieved.
2. According to the cylindrical lithium ion capacitor, the first diaphragm is added between the composite lithium source and the winding core, so that the effect of preventing the lithium source from being short-circuited with the positive electrode and the negative electrode is achieved.
3. According to the cylindrical lithium ion capacitor, the widths of the positive plate and the negative plate are limited, so that the path of lithium ions diffusing from the bottom to the top is relatively reduced, and the effects of improving the capacity and the cycle performance are achieved.
4. The preparation method of the cylindrical lithium ion capacitor provided by the invention is relatively simple in process, easy to operate and has a remarkable large-scale application prospect.
Drawings
FIG. 1 is a schematic diagram of a cylindrical lithium ion capacitor of the present invention;
FIG. 2 is a partial cross-sectional view of a winding core according to the present invention;
in the figure, 1, a capacitor case; 2. a composite lithium source; 3. a first diaphragm; 4. a winding core; 5. a foamed nickel layer; 6. a metallic lithium layer; 7. a positive plate; 8. a negative plate; 9. a rubber plug; 10. an aluminum foil layer; 11. a positive electrode active material; 12. a positive electrode tab; 13. a copper foil layer; 14. a negative electrode active material; 15. a negative electrode tab; 16. a second diaphragm.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
Example 1
A lithium ion capacitor comprises a hollow capacitor shell 1, and a composite lithium source 2, a first diaphragm 3 and a winding core 4 which are sequentially arranged in the inner cavity of the capacitor shell 1 from bottom to top; by adding the first diaphragm 3 between the composite lithium source 2 and the winding core 4, the effect of preventing the lithium source from being short-circuited with the positive electrode and the negative electrode is achieved. Wherein, the composite lithium source 2 is cylindrical, and the diameter of the composite lithium source is equal to that of the winding core 4; the first diaphragm 3 is cylindrical, has a thickness of 50-150 μm, and has a diameter equal to the inner diameter of the capacitor case 1; the material of the capacitor case 1 is steel, and the material of the first separator 3 includes at least one of polyethylene, polypropylene, and cellulose.
The composite lithium source 2 comprises a foamed nickel layer 5 and a metal lithium layer 6, wherein the foamed nickel layer 5 is welded with the bottom of the capacitor shell 1; through setting up compound lithium source 2 in the inner chamber bottom of capacitor case 1 for lithium ion is under the condition that need not the perforation, only relies on the effect of electric field force directly from lower supreme diffusion to negative pole piece 8 in, and the gap direct diffusion between rethread first diaphragm 3, positive plate 7 and the negative pole piece 8 reaches the negative pole of whole condenser, has reached under the condition of guaranteeing cyclicity and capacity, avoids using the effect of expensive perforation copper, aluminium foil and complicated coating technology.
The winding core 4 is formed by winding a positive plate 7, a second diaphragm 16 and a negative plate 8 which are arranged at intervals, and a rubber plug 9 is arranged at the upper end of the winding core 4; the positive plate 7 comprises an aluminum foil layer 10, a positive active material 11 and a positive tab 12, wherein the positive active material 11 is uniformly coated on the outer surface of the aluminum foil layer 10, and the positive tab 12 is positioned at the upper end of the aluminum foil layer 10; the negative plate 8 comprises a copper foil layer 13, a negative active material 14 and a negative tab 15, wherein the negative active material 14 is uniformly coated on the outer surface of the copper foil layer 13, and the negative tab 15 is positioned at the upper end of the copper foil layer 13;
the width of the positive plate 7 is 6-30 mm, the positive active material 11 is activated carbon, and the material of the positive tab 12 is aluminum; the width of the negative plate 8 is 6-30 mm, the negative active material 14 comprises one or more of graphite, hard carbon and soft carbon, and the material of the negative tab 15 is copper; the width of the positive plate 7 and the negative plate 8 is limited, so that the path of lithium ions diffusing from the bottom to the top is relatively reduced, and the effects of improving the capacity and the cycle performance are achieved. The material of the second separator 16 includes one or more of polyethylene, polypropylene, and cellulose.
The implementation principle of the embodiment is as follows: the lithium is pre-embedded into the negative electrode through the composite lithium source 2 at the bottom of the capacitor shell 1, so that lithium ions are diffused to the negative plate 8 from the bottom of the winding core 4 under the action of an electric field force and then directly diffused to the negative electrode of the whole capacitor through gaps among the first diaphragm 3, the positive plate 7 and the negative plate 8; at this time, the negative electrode potential to lithium is lowered after lithium pre-intercalation, thereby achieving the effect of increasing the operating voltage of the lithium ion capacitor. When the lithium ion capacitor is charged, lithium ions in the organic electrolyte are embedded into the negative plate 8, and anions in the organic electrolyte are adsorbed on the positive plate 7; upon discharge, anions are released from the surface of the positive electrode sheet 7 back to the electrolyte, and lithium ions are extracted from the negative electrode sheet 8 back to the electrolyte.
Example 2
A method of making a lithium ion capacitor comprising the steps of:
s1-1, preparing the positive plate 7, which comprises the following steps:
A1. sequentially adding a thickening agent CMC, a conductive agent Super P, a positive active material 11, activated carbon YP-50F and a binding agent SBR into water in a mass ratio of 1.5:8:85:5.5, wherein the stirring time is 1h after each material is added, and finally obtaining a slurry I with the viscosity of 1100 cP;
A2. the slurry I was uniformly coated on the outer surface of the aluminum foil layer 10 using a coater, the density of the coated surface being 1.2g/dm2Drying and cutting by a pair of rollers to obtain a pole piece I to be welded with the width of 6mm, the length of 118mm and the thickness of 0.240 mm;
A3. welding a positive electrode tab 12 made of aluminum at the upper end of the pole piece I to be welded to obtain the electrode;
s1-2, preparing the negative plate 8, which comprises the following steps:
B1. sequentially adding a thickening agent CMC, a conductive agent Super P, a negative active material 14 hard carbon LN-002 and a binding agent SBR into water according to the mass ratio of 1.2:1.3:94:3.5, wherein the stirring time is 1h after each material is added, and finally obtaining a slurry II with the viscosity of 1200 cP;
B2. the slurry II was uniformly applied to the outer surface of the copper foil layer 13 using a coater, the density of the coated surface being 0.9g/dm2Drying and cutting with a pair of rollers to obtain a pole piece II to be welded, wherein the pole piece II is 8mm in width, 147mm in length and 0.1mm in thickness;
B3. and welding a negative pole lug 15 made of copper at the upper end of the pole piece II to be welded to obtain the electrode.
S1-3. preparation of composite lithium source 2: carrying out composite rolling on the foamed nickel and the metal lithium with the thickness of 0.19mm by using a roller press, and punching into a wafer with the diameter of 9mm to obtain the nickel-lithium battery;
s1-4, preparation of core 4: winding the negative pole piece 8, the second diaphragm 16 and the positive pole piece 7 which are sequentially arranged at intervals and have the widths of 8mm, 10mm and 6mm, fixing the negative pole piece, the second diaphragm 16 and the positive pole piece 7 by using an adhesive tape to obtain a cylindrical battery cell with the diameter of 9mm, and heating and drying the cylindrical battery cell to obtain a winding core 4;
s2, installing the rubber plug 9 on the top of the winding core 4 in a drying room or a glove box with a moisture dew point of-45 ℃ to-60 ℃ to obtain a winding core to be installed;
s3, welding a foamed nickel layer 5 of the composite lithium source 2 with the bottom of the capacitor shell 1 by using a single-needle spot welding machine, and sequentially placing the first diaphragm 3 and a winding core to be installed to obtain a shell to be processed;
s4, injecting organic electrolyte (lithium hexafluorophosphate LiPF6) into the to-be-treated shell, carrying out roller groove and sealing treatment, and standing at 40 ℃ for 48 hours to obtain a to-be-treated capacitor;
s5, pre-embedding lithium: respectively connecting the positive electrode and the negative electrode of a constant current charge-discharge tester with a negative electrode tab 15 of a capacitor to be processed and a capacitor shell 1, and discharging to 75% of the first discharge capacity of the negative electrode (the current is 0.622mA, and the discharge time is 30h) under the condition of setting the current of 0.025C in the working step to obtain a pre-embedded lithium capacitor;
s6, the pre-embedded lithium capacitor is placed into a heat-shrinkable sleeve to be heated and molded, and the lithium ion capacitor is obtained.
Example 3
A method of making a lithium ion capacitor comprising the steps of:
s1-1, preparing the positive plate 7, which comprises the following steps:
A1. sequentially adding a thickening agent CMC, a conductive agent Super P, a positive active material 11, activated carbon YP-50F and a binding agent SBR into water in a mass ratio of 1.5:8:85:5.5, wherein the stirring time is 1h after each material is added, and finally obtaining a slurry I with the viscosity of 1100 cP;
A2. the slurry I was uniformly coated on the outer surface of the aluminum foil layer 10 using a coater, the density of the coated surface being 1.2g/dm2Drying and cutting by a pair of rollers to obtain a pole piece I to be welded with the width of 6mm, the length of 118mm and the thickness of 0.240 mm;
A3. welding a positive electrode tab 12 made of aluminum at the upper end of the pole piece I to be welded to obtain the electrode;
s1-2, preparing the negative plate 8, which comprises the following steps:
B1. sequentially adding a thickening agent CMC, a conductive agent Super P, a negative active material 14 hard carbon LN-002 and a binding agent SBR into water according to the mass ratio of 1.2:1.3:94:3.5, wherein the stirring time is 1h after each material is added, and finally obtaining a slurry II with the viscosity of 1200 cP;
B2. the slurry II was uniformly applied to the outer surface of the copper foil layer 13 using a coater, the density of the coated surface being 0.9g/dm2Drying and cutting with double rollers to obtain the product with width of 8mm, length of 147mm and thickness of 01mm pole piece II to be welded;
B3. and welding a negative pole lug 15 made of copper at the upper end of the pole piece II to be welded to obtain the electrode.
S1-3. preparation of composite lithium source 2: carrying out composite rolling on the foamed nickel and the metal lithium with the thickness of 0.19mm by using a roller press, and punching into a wafer with the diameter of 9mm to obtain the nickel-lithium battery;
s1-4, preparation of core 4: winding the negative pole piece 8, the second diaphragm 16 and the positive pole piece 7 which are sequentially arranged at intervals and have the widths of 8mm, 10mm and 6mm, fixing the negative pole piece, the second diaphragm 16 and the positive pole piece 7 by using an adhesive tape to obtain a cylindrical battery cell with the diameter of 9mm, and heating and drying the cylindrical battery cell to obtain a winding core 4;
s2, installing the rubber plug 9 on the top of the winding core 4 in a drying room or a glove box with a moisture dew point of-45 ℃ to-60 ℃ to obtain a winding core to be installed;
s3, welding a foamed nickel layer 5 of the composite lithium source 2 with the bottom of the capacitor shell 1 by using a single-needle spot welding machine, and sequentially placing the first diaphragm 3 and a winding core to be installed to obtain a shell to be processed;
s4, injecting organic electrolyte (lithium hexafluorophosphate LiPF6) into the to-be-treated shell, carrying out roller groove and sealing treatment, and standing at 40 ℃ for 48 hours to obtain a to-be-treated capacitor;
s5, pre-embedding lithium: respectively connecting the positive electrode and the negative electrode of a constant current charge-discharge tester with a negative electrode tab 15 of the capacitor to be processed and a capacitor shell 1, discharging to 90% of the first discharge capacity of the negative electrode (the current is 0.622mA, the discharge time is 36h) under the condition of setting the current of 0.025C in the working step, and placing for 24h at 45 ℃ to obtain a pre-embedded lithium capacitor;
s6, the pre-embedded lithium capacitor is placed into a heat-shrinkable sleeve to be heated and molded, and the lithium ion capacitor is obtained.
Example 4
A method of making a lithium ion capacitor comprising the steps of:
s1-1, preparing the positive plate 7, which comprises the following steps:
A1. sequentially adding a thickening agent CMC, a conductive agent Super P, a positive active material 11, activated carbon YP-50F and a binding agent SBR into water in a mass ratio of 1.5:8:85:5.5, wherein the stirring time is 2 hours after each material is added, and finally obtaining a slurry I with the viscosity of 1500 cP;
A2. the slurry I was uniformly coated on the outer surface of the aluminum foil layer 10 using a coater, the density of the coated surface being 1.2g/dm2Drying and cutting by a pair of rollers to obtain a pole piece I to be welded, wherein the width of the pole piece I is 18mm, the length of the pole piece I is 118mm, and the thickness of the pole piece I is 0.240 mm;
A3. welding a positive electrode tab 12 made of aluminum at the upper end of the pole piece I to be welded to obtain the electrode;
s1-2, preparing the negative plate 8, which comprises the following steps:
B1. sequentially adding a thickening agent CMC, a conductive agent Super P, a negative active material 14 hard carbon LN-002 and a binding agent SBR into water in a mass ratio of 1.2:1.3:94:3.5, wherein the stirring time is 2 hours after each material is added, and finally obtaining a slurry II with the viscosity of 1600 cP;
B2. the slurry II was uniformly applied to the outer surface of the copper foil layer 13 using a coater, the density of the coated surface being 0.9g/dm2Drying and cutting with a pair of rollers to obtain a pole piece II to be welded, wherein the pole piece II is 20mm in width, 147mm in length and 0.1mm in thickness;
B3. and welding a negative pole lug 15 made of copper at the upper end of the pole piece II to be welded to obtain the electrode.
S1-3. preparation of composite lithium source 2: carrying out composite rolling on the foamed nickel and the metal lithium with the thickness of 0.47mm by using a roller press, and punching into a wafer with the diameter of 9mm to obtain the nickel-lithium battery;
s1-4, preparation of core 4: winding the negative pole piece 8, the second diaphragm 16 and the positive pole piece 7 which are sequentially arranged at intervals and have the widths of 20mm, 22mm and 18mm, fixing the negative pole piece, the second diaphragm 16 and the positive pole piece by using an adhesive tape to obtain a cylindrical battery cell with the diameter of 9mm, and heating and drying the cylindrical battery cell to obtain a winding core 4;
s2, installing the rubber plug 9 on the top of the winding core 4 in a drying room or a glove box with a moisture dew point of-45 ℃ to-60 ℃ to obtain a winding core to be installed;
s3, welding a foamed nickel layer 5 of the composite lithium source 2 with the bottom of the capacitor shell 1 by using a single-needle spot welding machine, and sequentially placing the first diaphragm 3 and a winding core to be installed to obtain a shell to be processed;
s4, injecting organic electrolyte (lithium hexafluorophosphate LiPF6) into the to-be-treated shell, carrying out roller groove and sealing treatment, and standing at 45 ℃ for 36h to obtain a to-be-treated capacitor;
s5, pre-embedding lithium: respectively connecting the positive electrode and the negative electrode of a constant current charge-discharge tester with a negative electrode tab 15 of a capacitor to be processed and a capacitor shell 1, and discharging to 75% of the first discharge capacity of the negative electrode (the current is 1.55mA, and the discharge time is 30h) under the condition of setting the current of 0.025C in the working step to obtain a pre-embedded lithium capacitor;
s6, the pre-embedded lithium capacitor is placed into a heat-shrinkable sleeve to be heated and molded, and the lithium ion capacitor is obtained.
Example 5
A method of making a lithium ion capacitor comprising the steps of:
s1-1, preparing the positive plate 7, which comprises the following steps:
A1. sequentially adding a thickening agent CMC, a conductive agent Super P, a positive active material 11, activated carbon YP-50F and a binding agent SBR into water in a mass ratio of 1.5:8:85:5.5, wherein the stirring time is 2 hours after each material is added, and finally obtaining a slurry I with the viscosity of 1500 cP;
A2. the slurry I was uniformly coated on the outer surface of the aluminum foil layer 10 using a coater, the density of the coated surface being 1.2g/dm2Drying and cutting by a pair of rollers to obtain a pole piece I to be welded, wherein the width of the pole piece I is 18mm, the length of the pole piece I is 118mm, and the thickness of the pole piece I is 0.240 mm;
A3. welding a positive electrode tab 12 made of aluminum at the upper end of the pole piece I to be welded to obtain the electrode;
s1-2, preparing the negative plate 8, which comprises the following steps:
B1. sequentially adding a thickening agent CMC, a conductive agent Super P, a negative active material 14 hard carbon LN-002 and a binding agent SBR into water in a mass ratio of 1.2:1.3:94:3.5, wherein the stirring time is 2 hours after each material is added, and finally obtaining a slurry II with the viscosity of 1600 cP;
B2. the slurry II was uniformly applied to the outer surface of the copper foil layer 13 using a coater, the density of the coated surface being 0.9g/dm2Drying and cutting with a pair of rollers to obtain a pole piece II to be welded, wherein the pole piece II is 20mm in width, 147mm in length and 0.1mm in thickness;
B3. and welding a negative pole lug 15 made of copper at the upper end of the pole piece II to be welded to obtain the electrode.
S1-3. preparation of composite lithium source 2: carrying out composite rolling on the foamed nickel and the metal lithium with the thickness of 0.47mm by using a roller press, and punching into a wafer with the diameter of 9mm to obtain the nickel-lithium battery;
s1-4, preparation of core 4: winding the negative pole piece 8, the second diaphragm 16 and the positive pole piece 7 which are sequentially arranged at intervals and have the widths of 20mm, 22mm and 18mm, fixing the negative pole piece, the second diaphragm 16 and the positive pole piece by using an adhesive tape to obtain a cylindrical battery cell with the diameter of 9mm, and heating and drying the cylindrical battery cell to obtain a winding core 4;
s2, installing the rubber plug 9 on the top of the winding core 4 in a drying room or a glove box with a moisture dew point of-45 ℃ to-60 ℃ to obtain a winding core to be installed;
s3, welding a foamed nickel layer 5 of the composite lithium source 2 with the bottom of the capacitor shell 1 by using a single-needle spot welding machine, and sequentially placing the first diaphragm 3 and a winding core to be installed to obtain a shell to be processed;
s4, injecting organic electrolyte (lithium hexafluorophosphate LiPF6) into the to-be-treated shell, carrying out roller groove and sealing treatment, and standing at 45 ℃ for 36h to obtain a to-be-treated capacitor;
s5, pre-embedding lithium: respectively connecting the positive electrode and the negative electrode of a constant current charge-discharge tester with a negative electrode tab 15 of a capacitor to be processed and a capacitor shell 1, and discharging to 90% of the first discharge capacity of the negative electrode (the current is 1.55mA, and the discharge time is 36h) under the condition of setting the current of 0.025C in the working step to obtain a pre-embedded lithium capacitor;
s6, the pre-embedded lithium capacitor is placed into a heat-shrinkable sleeve to be heated and molded, and the lithium ion capacitor is obtained.
Example 6
A method of making a lithium ion capacitor comprising the steps of:
s1-1, preparing the positive plate 7, which comprises the following steps:
A1. sequentially adding a thickening agent CMC, a conductive agent Super P, a positive active material 11, activated carbon YP-50F and a binder SBR into water in a mass ratio of 1.5:8:85:5.5, wherein the stirring time is 3 hours after each material is added, and finally obtaining a slurry I with the viscosity of 2800 cP;
A2. the slurry I was uniformly coated on the outer surface of the aluminum foil layer 10 using a coater, the density of the coated surface being 1.2g/dm2Drying and cutting by a pair of rollers to obtain a pole piece I to be welded with the width of 28mm, the length of 118mm and the thickness of 0.240 mm;
A3. welding a positive electrode tab 12 made of aluminum at the upper end of the pole piece I to be welded to obtain the electrode;
s1-2, preparing the negative plate 8, which comprises the following steps:
B1. sequentially adding a thickening agent CMC, a conductive agent Super P, a negative active material 14 hard carbon LN-002 and a binding agent SBR into water according to the mass ratio of 1.2:1.3:94:3.5, wherein the stirring time is 3 hours after each material is added, and finally obtaining a slurry II with the viscosity of 2700 cP;
B2. the slurry II was uniformly applied to the outer surface of the copper foil layer 13 using a coater, the density of the coated surface being 0.9g/dm2Drying and cutting by a pair of rollers to obtain a pole piece II to be welded, wherein the pole piece II is 30mm in width, 147mm in length and 0.1mm in thickness;
B3. and welding a negative pole lug 15 made of copper at the upper end of the pole piece II to be welded to obtain the electrode.
S1-3. preparation of composite lithium source 2: carrying out composite rolling on the foamed nickel and the metal lithium with the thickness of 0.71mm by using a roller press, and punching into a wafer with the diameter of 9mm to obtain the nickel-lithium battery;
s1-4, preparation of core 4: winding the negative pole piece 8, the second diaphragm 16 and the positive pole piece 7 which are sequentially arranged at intervals and have the widths of 30mm, 32mm and 28mm, fixing the negative pole piece, the second diaphragm 16 and the positive pole piece 7 by using an adhesive tape to obtain a cylindrical battery cell with the diameter of 9mm, and heating and drying the cylindrical battery cell to obtain a winding core 4;
s2, installing the rubber plug 9 on the top of the winding core 4 in a drying room or a glove box with a moisture dew point of-45 ℃ to-60 ℃ to obtain a winding core to be installed;
s3, welding a foamed nickel layer 5 of the composite lithium source 2 with the bottom of the capacitor shell 1 by using a single-needle spot welding machine, and sequentially placing the first diaphragm 3 and a winding core to be installed to obtain a shell to be processed;
s4, injecting organic electrolyte (lithium hexafluorophosphate LiPF6) into the to-be-treated shell, carrying out roller groove and sealing treatment, and standing at 50 ℃ for 24 hours to obtain a to-be-treated capacitor;
s5, pre-embedding lithium: respectively connecting the positive electrode and the negative electrode of a constant current charge-discharge tester with a negative electrode tab 15 of a capacitor to be processed and a capacitor shell 1, and discharging to 75% of the first discharge capacity of the negative electrode (the current is 2.33mA, and the discharge time is 30h) under the condition of setting the current of 0.025C in the working step to obtain a pre-embedded lithium capacitor;
s6, the pre-embedded lithium capacitor is placed into a heat-shrinkable sleeve to be heated and molded, and the lithium ion capacitor is obtained.
Example 7
A method of making a lithium ion capacitor comprising the steps of:
s1-1, preparing the positive plate 7, which comprises the following steps:
A1. sequentially adding a thickening agent CMC, a conductive agent Super P, a positive active material 11, activated carbon YP-50F and a binder SBR into water in a mass ratio of 1.5:8:85:5.5, wherein the stirring time is 3 hours after each material is added, and finally obtaining a slurry I with the viscosity of 2800 cP;
A2. the slurry I was uniformly coated on the outer surface of the aluminum foil layer 10 using a coater, the density of the coated surface being 1.2g/dm2Drying and cutting by a pair of rollers to obtain a pole piece I to be welded with the width of 28mm, the length of 118mm and the thickness of 0.240 mm;
A3. welding a positive electrode tab 12 made of aluminum at the upper end of the pole piece I to be welded to obtain the electrode;
s1-2, preparing the negative plate 8, which comprises the following steps:
B1. sequentially adding a thickening agent CMC, a conductive agent Super P, a negative active material 14 hard carbon LN-002 and a binding agent SBR into water according to the mass ratio of 1.2:1.3:94:3.5, wherein the stirring time is 3 hours after each material is added, and finally obtaining a slurry II with the viscosity of 2700 cP;
B2. the slurry II was uniformly applied to the outer surface of the copper foil layer 13 using a coater, the density of the coated surface being 0.9g/dm2Drying and cutting by a pair of rollers to obtain a pole piece II to be welded, wherein the pole piece II is 30mm in width, 147mm in length and 0.1mm in thickness;
B3. and welding a negative pole lug 15 made of copper at the upper end of the pole piece II to be welded to obtain the electrode.
S1-3. preparation of composite lithium source 2: carrying out composite rolling on the foamed nickel and the metal lithium with the thickness of 0.71mm by using a roller press, and punching into a wafer with the diameter of 9mm to obtain the nickel-lithium battery;
s1-4, preparation of core 4: winding the negative pole piece 8, the second diaphragm 16 and the positive pole piece 7 which are sequentially arranged at intervals and have the widths of 30mm, 32mm and 28mm, fixing the negative pole piece, the second diaphragm 16 and the positive pole piece 7 by using an adhesive tape to obtain a cylindrical battery cell with the diameter of 9mm, and heating and drying the cylindrical battery cell to obtain a winding core 4;
s2, installing the rubber plug 9 on the top of the winding core 4 in a drying room or a glove box with a moisture dew point of-45 ℃ to-60 ℃ to obtain a winding core to be installed;
s3, welding a foamed nickel layer 5 of the composite lithium source 2 with the bottom of the capacitor shell 1 by using a single-needle spot welding machine, and sequentially placing the first diaphragm 3 and a winding core to be installed to obtain a shell to be processed;
s4, injecting organic electrolyte (lithium hexafluorophosphate LiPF6) into the to-be-treated shell, performing roller groove and sealing treatment, and standing at 45-50 ℃ for 24h to obtain a to-be-treated capacitor;
s5, pre-embedding lithium: respectively connecting the positive electrode and the negative electrode of a constant current charge-discharge tester with a negative electrode tab 15 of a capacitor to be processed and a capacitor shell 1, and discharging to 90% of the first discharge capacity of the negative electrode (the current is 2.33mA, and the discharge time is 36h) under the condition of setting the current of 0.025C in the working step to obtain a pre-embedded lithium capacitor;
s6, the pre-embedded lithium capacitor is placed into a heat-shrinkable sleeve to be heated and molded, and the lithium ion capacitor is obtained.
Comparative example 1
The lithium ion capacitor prepared in example 4 of the present invention was compared with comparative example 1, in which the preparation method of comparative example 1 was: the width of the negative plate is 40mm, the width of the positive plate is 38mm, the thickness of the metal lithium is 0.95mm, and the discharging current is 3.1mA during lithium pre-intercalation; the other conditions such as the amount, the procedure and the conditions are the same as those in example 6 of the present invention (in this comparative example, when the pre-intercalation capacity is 75% of the first discharge capacity of the negative electrode, the widths of the negative electrode plate and the positive electrode plate are compared with each other, which is used to prove that the performance of the lithium ion capacitor of the present invention is better).
Comparative example 2
The lithium ion capacitor prepared in the embodiment 5 of the invention is compared with the comparative example 2, wherein in the preparation method of the comparative example 2, the width of the negative plate is 40mm, the width of the positive plate is 38mm, the thickness of the metal lithium is 0.95mm, and the discharging current is 3.1mA during pre-lithium intercalation; the other conditions, such as the amount, the procedure and the conditions, were the same as those in example 7 of the present invention (in this comparative example, the widths of the negative electrode plate and the positive electrode plate were compared with each other when the pre-intercalation capacity was 90% of the first discharge capacity of the negative electrode, which was used to prove that the performance of the lithium ion capacitor of the present invention was better).
Comparative example 3
The lithium ion capacitor prepared in example 7 of the present invention is compared with comparative example 3, wherein in the preparation method of comparative example 3, step S3 specifically includes: welding a foamed nickel layer of the composite lithium source with the side wall of the capacitor shell by using a single-needle spot welding machine, and sequentially placing a first diaphragm and a to-be-installed winding core so that the composite lithium source and the to-be-installed winding core are adjacently placed and are separated by the first diaphragm; the other parameters such as the amount, the steps and the conditions are the same as those in example 7 of the present invention (the comparative example is compared with a composite lithium source mounted on the side wall of the capacitor case to prove that the performance of the lithium ion capacitor of the present invention is better).
Test effects
In order to verify the performance of the lithium ion capacitor of the present invention, the lithium ion capacitors prepared in examples 2 to 7 and comparative examples 1 to 3 were tested. The test method comprises the following steps: under the condition that the voltage is 2.2-3.8V, the lithium ion capacitors of each group are respectively subjected to 10C charge-discharge test capacity and cycle performance, and the results are shown in the following table:
group of Operating voltage V Capacity F of capacitor Gram capacity of positive electrode F/g Capacity retention at 5000 weeks%
Example 2 2.2-3.8 7.3 101 95.6
Example 3 2.2-3.8 7.9 110 95.7
Example 4 2.2-3.8 21.6 101 95.5
Example 5 2.2-3.8 23.8 110 95.5
Example 6 2.2-3.8 33.7 99 95.3
Example 7 2.2-3.8 37.1 110 95.4
Control group 1 2.2-3.8 36.5 80 89
Control group 2 2.2-3.8 41.1 90 90
Control group 3 2.2-3.8 12.3 36.6 10
As can be seen from the above table, compared with examples 6 to 7, the gram capacity and 5000-cycle capacity retention rate of the positive electrode of the control group 1 to 2 are significantly reduced, because when the widths of the negative electrode plate and the positive electrode plate are too large, lithium ions are difficult to diffuse from the bottom to the top under the action of an electric field force, so that lithium pre-insertion of the negative electrode of the lithium ion capacitor is insufficient, and effective lithium ions are insufficient, thereby causing the cycle performance and the capacity performance to be abnormal; compared with example 7, the gram-positive capacity and 5000-cycle capacity retention ratio of the positive electrode of the control group 3 are extremely low, because the lithium source is placed on the side surface of the capacitor shell, and lithium ions cannot penetrate through the positive plate and diffuse to the negative plate of the capacitor under the action of an electric field force, so that the lithium ions pre-embedded in the negative electrode are seriously insufficient, and the cycle performance and the capacity exertion are abnormal.
In conclusion, the cylindrical lithium ion capacitor disclosed by the invention achieves the effects of improving the cycle performance and capacity, shortening the preparation period and reducing the production cost, equipment requirements and manufacturing process difficulty.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (9)

1. A cylindrical lithium ion capacitor is characterized by comprising a cylindrical and hollow capacitor shell (1), and a composite lithium source (2), a first diaphragm (3) and a winding core (4) which are sequentially arranged in an inner cavity of the capacitor shell (1) from bottom to top;
the composite lithium source (2) comprises a foamed nickel layer (5) and a metal lithium layer (6), wherein the foamed nickel layer (5) is connected with the bottom of the capacitor shell (1);
the winding core (4) is formed by winding a positive plate (7), a second diaphragm (16) and a negative plate (8) which are arranged at intervals, and a rubber plug (9) is arranged at the upper end of the winding core (4);
the positive plate (7) comprises an aluminum foil layer (10), a positive active material (11) and a positive tab (12), wherein the positive active material (11) is uniformly coated on the outer surface of the aluminum foil layer (10), and the positive tab (12) is positioned at the upper end of the aluminum foil layer (10);
the negative plate (8) comprises a copper foil layer (13), a negative active material (14) and a negative tab (15), the negative active material (14) is uniformly coated on the outer surface of the copper foil layer (13), and the negative tab (15) is positioned at the upper end of the copper foil layer (13);
the width of the positive plate (7) is 6-30 mm, and the width of the negative plate (8) is 6-30 mm.
2. The cylindrical lithium ion capacitor according to claim 1, wherein the positive electrode active material (11) comprises activated carbon, and the material of the positive electrode tab (12) comprises aluminum; the negative active material (14) includes one or more of graphite, hard carbon, and soft carbon, and the material of the negative tab (15) includes copper.
3. The cylindrical lithium ion capacitor according to claim 1, wherein the material of the first separator (3) comprises at least one of polyethylene, polypropylene and cellulose, the material of the second separator (16) comprises one or more of polyethylene, polypropylene and cellulose, and the material of the capacitor housing (1) comprises steel.
4. The method for preparing the cylindrical lithium ion capacitor according to any one of claims 1 to 3, comprising the following steps:
s1, winding the negative pole piece (8), the second diaphragm (16) and the positive pole piece (7) which are sequentially arranged at intervals to obtain a cylindrical battery cell, and heating and drying to obtain a winding core (4);
s2, installing a rubber plug (9) at the top of the winding core (4) to obtain a winding core to be installed;
s3, welding a foam nickel layer (5) of the composite lithium source (2) with the bottom of the capacitor shell (1), and sequentially placing the first diaphragm (3) and a winding core to be installed to obtain a shell to be processed;
s4, injecting organic electrolyte into the to-be-treated shell, performing roller groove and sealing treatment, and standing at 40-50 ℃ for 24-48 h to obtain a to-be-treated capacitor;
s5, pre-embedding lithium into the negative electrode of the capacitor to be processed in a constant current discharging mode by taking the negative electrode as a working electrode and a metal lithium electrode as an auxiliary electrode to obtain a pre-embedded lithium capacitor;
s6, the pre-embedded lithium capacitor is subjected to heating forming treatment to obtain the lithium ion capacitor.
5. The method according to claim 4, wherein in S1, the method for preparing the positive electrode sheet (7) comprises the steps of:
s7, sequentially adding a thickening agent, a conductive agent, the positive active material (11) and an adhesive in a mass ratio of 1.5:8:85:5.5 into water, wherein the stirring time is 1-3 hours after each material is added, and finally obtaining slurry I with the viscosity of 1000-3000 cP;
s8, uniformly coating the slurry I on the outer surface of the aluminum foil layer (10), and then drying and carrying out double-roller cutting treatment to obtain a pole piece I to be welded;
and S9, welding the positive electrode lug (12) at the upper end of the pole piece I to be welded to obtain the electrode.
6. The method according to claim 5, wherein in S1, the preparation method of the negative electrode sheet (8) comprises the following steps:
s10, sequentially adding a thickening agent, a conductive agent, the negative active material (14) and a bonding agent into water in a mass ratio of 1.2:1.3:94:3.5, wherein the stirring time is 1-3 hours after each material is added, and finally obtaining slurry II with the viscosity of 1000-3000 cP;
s11, uniformly coating the slurry II on the outer surface of the copper foil layer (13), and drying and carrying out double-roller cutting treatment to obtain a pole piece II to be welded;
and S12, welding the negative pole lug (15) at the upper end of the pole piece II to be welded to obtain the electrode.
7. The method according to claim 5, wherein in S3, the composite lithium source (2) is prepared by composite rolling of foamed nickel and metallic lithium, and punching.
8. The method of claim 5, wherein in S4, the organic electrolyte comprises lithium hexafluorophosphate.
9. The method of claim 5, wherein in S5, the constant current is 0.01-0.05C, and the capacity of the pre-embedded lithium accounts for 75-90% of the first discharge capacity of the negative electrode.
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