CN114883531A - Three-electrode lithium ion battery and lithium pre-charging and lithium supplementing method thereof - Google Patents
Three-electrode lithium ion battery and lithium pre-charging and lithium supplementing method thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 107
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000001502 supplementing effect Effects 0.000 title claims description 8
- 239000013589 supplement Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 230000002093 peripheral effect Effects 0.000 claims abstract description 6
- 238000009830 intercalation Methods 0.000 claims description 10
- 230000002687 intercalation Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
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- 238000000576 coating method Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 239000011267 electrode slurry Substances 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
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- 239000011230 binding agent Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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Abstract
The invention discloses a three-electrode lithium ion battery, which comprises a composite electrode, wherein the composite electrode comprises a plurality of positive plates and negative plates which are alternately stacked, the area of each positive plate is smaller than that of each negative plate, a frame-shaped third electrode is arranged around the positive plates on the periphery of each positive plate, the frame-shaped third electrodes and the positive plates are positioned in the same plane, and the frame-shaped third electrodes are electrodes containing metal lithium. According to the invention, the frame-shaped third electrode is used for pre-lithium preparation and lithium supplement on the negative plate, so that the first coulomb efficiency and the cycle life of the lithium ion battery can be effectively improved. According to the invention, the frame-shaped third electrode is arranged on the peripheral side of the positive plate, so that the frame-shaped third electrode and the positive plate are in the same plane, on one hand, the thickness of the battery is not increased due to the additionally added third electrode, and the volume of the battery is not increased; on the other hand, the third electrode with the structural design can be in direct contact with the negative plates on the two sides of the positive plate, so that the lithium ion transfer efficiency in the lithium pre-preparing process is improved, and the lithium pre-preparing time is shortened.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a three-electrode lithium ion battery and a lithium pre-charging and lithium supplementing method thereof.
Background
With the development of new energy electric vehicles and energy storage equipment, the market puts higher and higher requirements on the energy density and the quick charging performance of power lithium ion batteries. However, in the first charge and discharge process of the lithium ion battery, the electrolyte is subjected to reductive decomposition on the surfaces of the positive electrode and the negative electrode to generate a solid electrolyte film, namely an SEI film, and the generated SEI film prevents the active electrode from directly contacting the electrolyte, so that the cycle life of the lithium ion battery is prolonged. However, the SEI film generation consumes active Li + extracted from the positive electrode, resulting in a loss of battery capacity and a decrease in the first efficiency of lithium ion charging and discharging. When the surface area of the anode material is large, the amount of active lithium consumed is larger. In addition, when the lithium ion negative electrode adopts silicon base, the lithium ion can react with the silicon base negative electrode to generate an irreversible phase, and the first coulombic efficiency is further reduced. In order to solve the above problems, pre-lithium or lithium supplement for lithium ion batteries has become a research hotspot for scholars and large enterprises.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention aims to provide a three-electrode lithium ion battery and a lithium pre-charging and lithium supplementing method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a three-electrode lithium ion battery comprises a composite electrode, wherein the composite electrode comprises a plurality of positive plates and negative plates which are alternately stacked, and an isolating membrane is arranged between every two adjacent positive plates and negative plates; the area of the positive plate is smaller than that of the negative plate, the peripheral side of the positive plate is provided with a frame-shaped third electrode around the positive plate, the frame-shaped third electrode and the positive plate are positioned in the same plane, and the area of a plane formed by splicing the frame-shaped third electrode and the positive plate is not larger than that of the negative plate; the frame-shaped third electrode and the positive plate and the frame-shaped third electrode and the negative plate are isolated by isolation films; the frame-shaped third electrode is an electrode containing metallic lithium. Preferably, the frame-shaped third electrode is a lithium copper composite tape; the negative plate comprises a negative current collector and a negative material active layer loaded on the surface of the negative current collector, wherein the negative material active layer contains a negative material, and the negative material is graphite, mesocarbon microbeads, soft carbon, hard carbon, simple substance silicon,SiO x At least one of; the three-electrode lithium ion battery is one of a soft package battery, a square aluminum shell battery and a cylindrical battery.
The invention also provides a lithium pre-charging and lithium supplementing method of the three-electrode lithium ion battery, which comprises the following steps:
s1, injecting liquid into the three-electrode battery, directly connecting the frame-shaped third electrode with the negative plate through a lead after the liquid injection is completed, standing for 10-72h for pre-lithium, wherein the step of standing pre-lithium is to perform micro short circuit pre-lithium through the potential difference between the third electrode and the negative plate, in addition, metal lithium can perform solid phase diffusion pre-lithium due to the potential difference, and the lead is disconnected after the pre-lithium is completed for formation;
s2, connecting the frame-shaped third electrode of the formed three-electrode battery with the negative plate through an external power supply, and embedding lithium into the negative plate through the external power supply to form a graphite metal lithium half battery, and directly embedding lithium into the negative electrode; and (4) after lithium intercalation is finished, carrying out capacity grading to obtain the pre-lithium three-electrode battery. Preferably, the current multiplying power of the external power supply is 0.01C-2C, and the lithium embedding amount of the negative pole piece by the external power supply is 1-30% of SOC; the first discharge multiplying power in the capacity grading process is 0.01C-2C.
Further, after the three-electrode battery is charged and discharged for multiple times, the frame-shaped third electrode is connected with the positive plate or the negative plate through an external power supply so as to embed lithium and supplement lithium to the positive plate or the negative plate; the current multiplying power of the external power supply is 0.01C-2C, and the lithium supplement amount is 1% -30% SOC. After many times of charging and discharging, for example, capacity fading (i.e., loss of active lithium) occurs for 1000 weeks, and the life of the battery is extended by lithium supplement.
The invention has the following beneficial effects:
according to the three-electrode lithium ion battery provided by the invention, the frame-shaped third electrode is used for pre-lithium preparation and lithium supplement on the negative plate, so that the first coulomb efficiency and the cycle life of the lithium ion battery can be effectively improved. According to the invention, the frame-shaped third electrode is arranged on the peripheral side of the positive plate, so that the frame-shaped third electrode and the positive plate are in the same plane, on one hand, the thickness of the battery is not increased due to the additionally added third electrode, and the volume of the battery is not increased; on the other hand, the third electrode with the structural design can be in direct contact with the negative plates on the two sides of the positive plate, so that the lithium ion transfer efficiency in the lithium pre-preparing process is improved, and the lithium pre-preparing time is shortened. In addition, the three-electrode battery adopted in the invention has simple structural design and operation, simple processes of lithium pre-charging and lithium supplementing, no need of dismantling or taking out the frame-shaped third electrode, no safety problem because the metal lithium on the frame-shaped third electrode can be consumed in the lithium supplementing process, and suitability for large-scale production and application.
Drawings
Fig. 1 is a schematic structural diagram of a composite electrode in a three-electrode lithium ion battery provided by the present invention;
FIG. 2 is a schematic structural view of a frame-shaped third electrode;
FIG. 3 is a graph comparing the cycle performance of the batteries obtained in example 1 and comparative example 1;
FIG. 4 is a graph comparing the cycle performance of the batteries obtained in example 4 and comparative example 2;
reference numerals: 1-positive plate, 2-negative plate and 3-frame-shaped third electrode.
Detailed Description
The present invention will be further described with reference to the following examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention. The starting materials or reagents used in the following examples are all commercially available products.
A three-electrode lithium ion battery comprises a composite electrode, the structural schematic diagram of the composite electrode refers to fig. 1 and fig. 2, the composite electrode comprises a plurality of positive plates 1 and negative plates 2 which are alternately stacked, and an isolating membrane is arranged between the adjacent positive plates 1 and negative plates 2, for clearly showing the arrangement relationship of the positive plates and the negative plates and simplifying the structure, the isolating membrane is not drawn in fig. 1, and other descriptions are not made because the isolating membrane is a conventional composition structure in the battery; the area of the positive plate 1 is smaller than that of the negative plate 2, the frame-shaped third electrode 3 is arranged around the positive plate on the periphery of the positive plate 1, the frame-shaped third electrode 3 and the positive plate 1 are positioned in the same plane, and the area of the plane formed by splicing the frame-shaped third electrode 3 and the positive plate 1 is not larger than that of the negative plate; the frame-shaped third electrode 3 and the positive plate 1 and the frame-shaped third electrode 3 and the negative plate 2 are isolated by isolating films; the frame-shaped third electrode is an electrode containing metallic lithium. In order to ensure the isolation effect between the frame-shaped third electrode and the positive electrode sheet or the negative electrode sheet, the isolation film may be directly coated on the outer peripheral side of the frame-shaped third electrode, and then the frame-shaped third electrode may be placed around the outer peripheral side of the positive electrode sheet in the positional relationship shown in fig. 1.
Example 1
The method for pre-lithium and lithium supplement of the three-electrode lithium ion battery comprises the following steps:
s1 LiFePO 4 The anode material, the conductive agent carbon black and the binder PVDF are mixed according to the mass ratio of 95.5: 2: 2.5 preparing slurry by using a solvent NMP, coating the slurry on a current collector with the thickness of 12 mu m, coating carbon aluminum foil, and rolling and baking to prepare the positive plate. The negative electrode sheet is obtained by coating the negative electrode slurry on a current collector copper foil with the thickness of 8 mu m, baking and rolling the current collector copper foil, wherein the negative electrode slurry is prepared from graphite, a conductive agent carbon black, a binder SBR and a thickening agent CMC by using water as a solvent according to the mass ratio of 96:1:1.2: 1.8. A third electrode taking the lithium copper composite belt as a frame; LiFePO 4 the/C three-electrode battery is assembled and liquid-filled and packaged into a laminated soft package battery according to a mode of a drawing, and the electrolyte used is 1.0MLiPF 6 Standing the battery for 10 hours, directly connecting a tab of a negative plate of the packaged battery with a tab of a frame-shaped third electrode by using a lead, standing for 36 hours at the temperature of 30 ℃ for pre-lithium, and disconnecting the lead for formation after the pre-lithium is finished;
s2, connecting the frame-shaped third electrode of the formed three-electrode battery with the negative plate through an external power supply, and embedding lithium into the negative plate through the external power supply; the rate of lithium intercalation is 0.01C, and the amount of lithium intercalation is 5% of the battery capacity. And (4) carrying out capacity grading after lithium embedding is finished, and discharging at 0.02C multiplying power for the first time in the capacity grading process to obtain the pre-lithium three-electrode battery.
Comparative example 1
In comparison with example 1, the battery of comparative example 1 did not include the frame-shaped third electrode, and the other processes were the same as in example 1.
The batteries prepared in example 1 and comparative example 1 were subjected to cycle performance test under the test conditions of 1C charge and discharge and a voltage interval of 2.0 to 3.65V, and the test results are shown in fig. 3. As can be seen from fig. 3, the first coulombic efficiency of the three-electrode battery prepared in example 1 was improved by 7% compared to the first coulombic efficiency of the battery in the comparative example; the pre-lithium three-electrode battery is subjected to charge-discharge cycling until the capacity retention rate of the battery reaches 104 percent (based on the initial capacity of a comparative example) in 500 weeks, and the capacity retention rate of the battery is improved by about 9 percent compared with the capacity retention rate of a conventional battery. The first coulombic efficiency and the cycling stability of the lithium ion battery are effectively improved by adopting the method for pre-lithium of the three-electrode battery to the negative electrode.
Example 2
A pre-lithium and lithium supplement method of a three-electrode lithium ion battery comprises the following steps:
s1 LiFePO 4 The anode material, the conductive agent carbon black and the binder PVDF are mixed according to the mass ratio of 95.5: 2: 2.5 preparing slurry by using a solvent NMP, coating the slurry on a current collector with the thickness of 12 mu m, coating carbon aluminum foil, and rolling and baking to prepare the positive plate. The negative electrode sheet is obtained by coating the negative electrode slurry on a current collector copper foil with the thickness of 8 mu m, baking and rolling the current collector copper foil, wherein the negative electrode slurry is prepared from graphite, a conductive agent carbon black, a binder SBR and a thickening agent CMC by using water as a solvent according to the mass ratio of 96:1:1.2: 1.8. LiFePO 4 the/C three-electrode battery is assembled and liquid-filled and packaged into a laminated soft package battery according to a mode of a drawing, and the electrolyte used is 1.0MLiPF 6 Standing the battery for 10 hours, directly connecting a tab of a negative plate of the packaged battery with a tab of a frame-shaped third electrode by using a lead, standing for 24 hours at the temperature of 30 ℃ for pre-lithium, and disconnecting the lead for formation after the pre-lithium is finished;
s2, connecting the frame-shaped third electrode of the formed three-electrode battery with the negative plate through an external power supply, and embedding lithium into the negative plate through the external power supply; the rate of lithium intercalation is 0.1C, and the amount of lithium intercalation is 2% of the battery capacity. And (4) carrying out capacity grading after lithium embedding is finished, and discharging at 0.05C rate for the first time in the capacity grading process to obtain the pre-lithium three-electrode battery.
Example 3
A pre-lithium and lithium supplement method of a three-electrode lithium ion battery comprises the following steps:
s1 LiFePO 4 Positive electrode material, conductive agent carbon black, binderPVDF serving as a solvent is mixed according to the mass ratio of 95.5: 2: 2.5 preparing slurry by using a solvent NMP, coating the slurry on a current collector with the thickness of 12 mu m, coating carbon aluminum foil, and rolling and baking to prepare the positive plate. The negative electrode sheet is obtained by coating the negative electrode slurry on a current collector copper foil with the thickness of 8 mu m, baking and rolling the current collector copper foil, wherein the negative electrode slurry is prepared from graphite, a conductive agent carbon black, a binder SBR and a thickening agent CMC by using water as a solvent according to the mass ratio of 96:1:1.2: 1.8. LiFePO 4 the/C three-electrode battery is assembled and liquid-filled and packaged into a laminated soft package battery according to a mode of a drawing, and the electrolyte used is 1.0MLiPF 6 Standing the battery for 10 hours, directly connecting a tab of a negative plate of the packaged battery with a tab of a frame-shaped third electrode by using a lead, standing for 36 hours at the temperature of 30 ℃ for pre-lithium, and disconnecting the lead for formation after the pre-lithium is finished;
s2, connecting the frame-shaped third electrode of the formed three-electrode battery with the negative plate through an external power supply, and embedding lithium into the negative plate through the external power supply; the rate of lithium intercalation is 0.01C, and the amount of lithium intercalation is 4% of the battery capacity. And (4) carrying out capacity grading after lithium embedding is finished, and discharging at 0.01C multiplying power for the first time in the capacity grading process to obtain the pre-lithium three-electrode battery.
Example 4
A pre-lithium and lithium supplement method of a three-electrode lithium ion battery comprises the following steps:
s1 LiFePO 4 The anode material, the conductive agent carbon black and the binder PVDF are mixed according to the mass ratio of 95.5: 2: 2.5 preparing slurry by using a solvent NMP, coating the slurry on a current collector with the thickness of 12 mu m, coating carbon aluminum foil, and rolling and baking to prepare the positive plate. The negative electrode sheet is obtained by coating the negative electrode slurry on a current collector copper foil with the thickness of 8 mu m, baking and rolling the current collector copper foil, wherein the negative electrode slurry is prepared from graphite, a conductive agent carbon black, a binder SBR and a thickening agent CMC by using water as a solvent according to the mass ratio of 96:1:1.2: 1.8. LiFePO 4 the/C three-electrode battery is assembled and liquid-filled and packaged into a laminated soft package battery according to a mode of a drawing, and the electrolyte used is 1.0MLiPF 6 Standing the battery for 10 hours, directly connecting a tab of a negative plate of the packaged battery with a tab of a frame-shaped third electrode by using a lead, standing for 36 hours at the temperature of 30 ℃ for pre-lithium, and disconnecting the lead for formation after the pre-lithium is finished;
s2, connecting the frame-shaped third electrode of the formed three-electrode battery with the negative plate through an external power supply, and embedding lithium into the negative plate through the external power supply; the rate of lithium intercalation is 0.01C, and the amount of lithium intercalation is 6% of the battery capacity. And (4) carrying out capacity grading after lithium embedding is finished, and discharging at 0.01C multiplying power for the first time in the capacity grading process to obtain the pre-lithium three-electrode battery.
And S3, after the battery obtained in the step S2 is cycled for 1500 weeks (particularly the capacity retention rate is reduced by more than or equal to 5%), stopping charging and discharging, connecting the frame-shaped third electrode of the three-electrode battery with the positive plate through an external power supply, and embedding lithium into the positive plate through the external power supply, wherein the lithium embedding multiplying power is 0.01C, and the lithium embedding amount is 4% of the existing capacity of the battery. And continuing to perform charge-discharge circulation after the lithium supplement is finished.
Comparative example 2
In comparison with example 4, the battery of comparative example 2 did not include the frame-shaped third electrode, and the other processes were the same as in example 4.
The batteries prepared in example 4 and comparative example 2 were subjected to cycle performance test under the test conditions of 1C charge and discharge and a voltage interval of 2.0-3.65V, and the test results are shown in fig. 4. As can be seen from fig. 4, the first coulombic efficiency of the three-electrode battery prepared in example 4 was increased by 5.5% as compared with the first efficiency of the battery in comparative example 2; the capacity retention rate of the pre-lithium three-electrode battery is 98.5 percent (based on the initial capacity of the comparative example 2) after the pre-lithium three-electrode battery is cycled to 1500 weeks, and the capacity retention rate is improved by about 10 percent compared with the conventional battery. After 1500 weeks of cycling, the battery of example 4 was lithium-supplemented by 4%, and the capacity retention was 100% (based on the initial capacity of comparative example 2) and 17% higher than that of the conventional battery by 1976 weeks. The method for pre-lithium and lithium supplement of the negative electrode of the three-electrode battery greatly improves the first coulombic efficiency and the cycling stability of the lithium ion battery.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A three-electrode lithium ion battery is characterized in that: the composite electrode comprises a plurality of positive plates and negative plates which are alternately stacked, and an isolating film is arranged between every two adjacent positive plates and negative plates; the peripheral side of the positive plate is provided with a frame-shaped third electrode around the positive plate, and the area of a plane formed by splicing the frame-shaped third electrode and the positive plate is not larger than that of the negative plate; the frame-shaped third electrode is an electrode containing metallic lithium.
2. The three-electrode lithium ion battery of claim 1, wherein: an isolating film is arranged between the frame-shaped third electrode and the positive plate, and an isolating film is arranged between the frame-shaped third electrode and the negative plate.
3. The three-electrode lithium ion battery of claim 1, wherein: the frame-shaped third electrode is a lithium copper composite tape.
4. The three-electrode lithium ion battery of claim 1, wherein: the negative plate comprises a negative current collector and a negative material active layer loaded on the surface of the negative current collector, wherein the negative material active layer contains a negative material, and the negative material is graphite, mesocarbon microbeads, soft carbon, hard carbon, simple substance silicon and SiO x At least one of (1).
5. The three-electrode lithium ion battery of any one of claims 1 to 4, wherein: the three-electrode lithium ion battery is one of a soft package battery, a square aluminum shell battery and a cylindrical battery.
6. A pre-lithium and lithium supplementing method of a three-electrode lithium ion battery, wherein the three-electrode lithium ion battery is the three-electrode lithium ion battery of any one of claims 1 to 4, and is characterized in that: the method comprises the following steps:
s1, injecting liquid into the three-electrode battery, directly connecting the frame-shaped third electrode with the negative plate through a lead after the liquid injection is finished, standing for 10-72h for pre-lithium, and disconnecting the lead after the pre-lithium is finished for formation;
s2, connecting the frame-shaped third electrode of the formed three-electrode battery with the negative plate through an external power supply, and embedding lithium into the negative plate through the external power supply; and (4) carrying out capacity grading after lithium intercalation is finished to obtain the pre-lithium three-electrode battery.
7. The pre-lithium and lithium supplement method of a three-electrode lithium ion battery according to claim 6, characterized in that: in the step S2, the current multiplying power of the external power supply is 0.01C-2C, and the lithium embedding amount of the negative pole piece by the external power supply is 1-30% SOC; the first discharge multiplying power in the capacity grading process is 0.01-2C.
8. The pre-lithium and lithium supplement method of a three-electrode lithium ion battery according to claim 6, characterized in that: after the three-electrode battery is charged and discharged for multiple times, the frame-shaped third electrode is connected with the positive plate or the negative plate through the external power supply so as to embed lithium and supplement lithium for the positive plate or the negative plate; the current multiplying power of the external power supply is 0.01C-2C, and the lithium supplement amount is 1% -30% SOC.
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