CN111987379A - Lithium ion battery with reference electrode and preparation method thereof - Google Patents
Lithium ion battery with reference electrode and preparation method thereof Download PDFInfo
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- CN111987379A CN111987379A CN202010962046.7A CN202010962046A CN111987379A CN 111987379 A CN111987379 A CN 111987379A CN 202010962046 A CN202010962046 A CN 202010962046A CN 111987379 A CN111987379 A CN 111987379A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 117
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 115
- 238000004804 winding Methods 0.000 claims abstract description 111
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011889 copper foil Substances 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 13
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical group [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000003466 welding Methods 0.000 claims description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 210000004027 cell Anatomy 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- -1 polypropylene Polymers 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium ion battery with a reference electrode and a preparation method thereof. The lithium ion battery is provided with a reference pole piece outside the cathode pole piece at the outermost layer of the winding core. The reference pole piece includes a reference pole base layer and a reference pole lithium layer disposed on the reference pole base layer. The reference electrode base layer is a copper foil. The reference lithium layer is a lithium film. The negative pole piece on the outermost layer of the winding core is separated from the reference pole lithium layer through a winding core diaphragm. The reference electrode base layer is connected with a reference electrode tab, and is connected with a reference electrode pole on the battery shell through the reference electrode tab. According to the invention, whether lithium analysis exists in the negative electrode of the lithium ion battery is determined by referring to the voltage and impedance change between the positive electrode and the negative electrode, and whether the lithium ion battery fails is further judged according to the lithium analysis.
Description
Technical Field
The present invention relates to lithium ion batteries.
Background
The lithium ion battery has a limited service life, and the performance of the lithium ion battery gradually deteriorates as the number of times of the cycle charge and discharge of the lithium ion battery increases. The number of times of cyclic charge and discharge of a general lithium ion battery is 500-700 times, the number of times of cyclic charge and discharge of a lithium ion battery with a positive electrode made of a nickel cobalt lithium manganate ternary material is 2000-3000 times, and the number of times of cyclic charge and discharge of a lithium ion battery with a positive electrode made of lithium iron phosphate is 3000-6000 times. Under harsh environments, the number of times a lithium ion battery can be cycled may be less. The main reason for this deterioration of the lithium ion battery performance is that lithium ions precipitate out metallic lithium on the negative electrode during the charge and discharge of the lithium ion battery. With the increase of the number of times of sufficient electricity circulation, lithium ions are more and more precipitated at the negative electrode, so that the performance of the lithium ion battery is gradually reduced, mainly represented by the fact that the charging time is longer, the temperature is increased in the discharging process, and the like. In extreme cases, lithium metal precipitated from the negative electrode crystallizes to form lithium dendrites which penetrate the separator between the positive and negative electrodes, causing short circuits and causing fires and even explosions.
In the prior art, the performance of the lithium ion battery is generally monitored by detecting the voltages of the positive electrode and the negative electrode. However, this does not actually reflect the state of lithium ions, and particularly, the deposition of lithium ions in the negative electrode cannot be monitored. Patent document CN 111077455 a discloses a lithium analysis detection method for soft package lithium ion batteries. This document describes that a copper foil is folded in half, immersed in concentrated sulfuric acid for 3 to 5 minutes, dried, and then placed in a lithium ion battery as a reference electrode, and then lithium is separated out by a voltage difference between a negative electrode and the reference electrode. However, it has been found that the copper foil dissolves after being placed in concentrated sulfuric acid and then does not.
Disclosure of Invention
The problems to be solved by the invention are as follows: and monitoring the lithium ion precipitation condition of the lithium ion battery negative electrode.
In order to solve the problems, the invention adopts the following scheme:
the lithium ion battery with the reference electrode comprises a shell and a winding core arranged in the shell; the winding core is formed by laminating or winding a positive pole piece, a winding core diaphragm and a negative pole piece; the positive pole piece and the negative pole piece are respectively connected with a positive pole post and a negative pole post which are arranged on the shell through a positive pole lug and a negative pole lug; the reference pole piece is arranged in the shell; the reference pole piece comprises a reference pole lithium layer; the outermost layer of the winding core is the negative pole piece coated by the winding core diaphragm; the reference pole piece is tightly attached to the winding core, so that the reference pole lithium layer is separated from the negative pole piece through the winding core diaphragm, and the reference pole piece is coated by the reference pole diaphragm; the reference pole lithium layer is connected with a reference pole lug and is connected with a reference pole arranged on the shell through the reference pole lug, and the reference pole lithium layer is made of metal lithium.
Further, according to the lithium ion battery with the reference electrode, the lithium layer of the reference electrode is a lithium film with the thickness of 10-30 micrometers and the area of not less than 1 square centimeter.
Further, according to the lithium ion battery with the reference electrode, the reference electrode piece further comprises a reference electrode substrate layer; the reference electrode substrate layer is made of a conductive material; the reference electrode lithium layer is disposed on the reference electrode base layer; the reference pole base layer is connected with the reference pole tab.
Further, according to the lithium ion battery with the reference electrode of the present invention, the reference electrode lithium layer is smaller in size than the reference electrode base layer, and the reference electrode base layer is smaller than the reference electrode separator, so that the reference electrode lithium layer is covered by the reference electrode base layer, and the reference electrode base layer is covered by the reference electrode separator.
Further, according to the lithium ion battery with the reference electrode, the reference electrode base layer is made of copper foil.
Further, according to the lithium ion battery with the reference electrode, the winding core diaphragm comprises an outer winding core diaphragm and an inner winding core diaphragm; the winding core is formed by sequentially laminating and winding an outer layer winding core diaphragm, a negative pole piece, an inner layer winding core diaphragm and a positive pole piece; the reference electrode lithium layer is separated from the negative electrode pole piece through the outer layer coiled core diaphragm.
Further, according to the lithium ion battery with the reference electrode, the winding core is formed by alternately laminating the positive electrode pole piece and the negative electrode pole piece; the positive pole piece and the negative pole piece are separated by the winding core diaphragm.
Further, according to the lithium ion battery with the reference electrode, the positive electrode piece comprises a positive electrode substrate layer and a positive electrode active layer arranged on the positive electrode substrate layer; the positive electrode active layer is made of active lithium; the negative pole piece comprises a negative pole substrate layer and a negative pole active layer arranged on the negative pole substrate layer;
further, according to the lithium ion battery with the reference electrode, the active lithium is nickel cobalt lithium manganate or lithium iron phosphate.
The preparation method of the lithium ion battery with the reference electrode is used for preparing the lithium ion battery with the reference electrode and comprises the steps of preparing a winding core, preparing a battery core and assembling, injecting and sealing; the step of preparing the winding core is used for preparing the winding core;
wherein the step of preparing the battery cell comprises:
step S21: rolling a lithium belt with the thickness of 100 microns on a release film into a lithium film with the thickness of 10-30 microns to obtain a laminated sheet of the release film and the lithium film;
step S22: stacking the laminated sheet of the release film and the lithium film on a copper foil with the thickness of 4.5-30 micrometers, and applying a pressure of 8.0-10.0 kilopascals to transfer the lithium film on the laminated sheet of the release film and the lithium film to the copper foil to obtain a reference pole piece formed by stacking the lithium film and the copper foil;
step S23: welding a reference pole lug on a copper foil of a reference pole piece formed by overlapping the lithium film and the copper foil;
step S24: attaching a reference pole piece formed by overlapping the lithium film and the copper foil to the surface of the winding core in a manner that the lithium film faces the inner side, so that the lithium film is separated from a negative pole piece of the winding core through a winding core diaphragm and is covered by the reference pole diaphragm, and thus obtaining an electric core consisting of the winding core and the reference pole piece;
and the step of assembling, injecting and sealing is used for packaging the prepared battery core and the electrolyte into the shell.
The invention has the following technical effects: the invention introduces a reference electrode mainly made of a lithium film into a lithium ion battery. After the negative electrode is reduced to metallic lithium and deposited, the voltage of the positive electrode and the negative electrode with respect to the reference electrode gradually decreases, and the resistance impedances between the positive electrode and the reference electrode and between the negative electrode and the reference electrode increase. Therefore, whether the lithium ion battery analyzes lithium or not is judged according to the voltage change and the resistance impedance change, or whether the lithium ion battery fails or not is further judged according to the voltage change and the resistance impedance change.
Drawings
Fig. 1 is a schematic structural diagram of an embodiment of a circular wound cell of a lithium ion battery of the present invention.
Fig. 2 is a schematic diagram of the overall structure of the lithium ion battery with a circular winding core.
Fig. 3 is a schematic structural diagram of an embodiment of a flat winding cell of a lithium ion battery according to the present invention.
Fig. 4 is a schematic structural diagram of an embodiment of a laminated cell of a lithium ion battery of the present invention.
Fig. 5 and 6 are schematic structural views of the positive electrode tab and the negative electrode tab, respectively.
Wherein the content of the first and second substances,
100 is a winding core, 200 is a reference pole piece;
11 is a positive pole piece, 12 is a negative pole piece, and 13 is a roll core diaphragm;
110 is a positive electrode base layer, 111 is a positive electrode base portion, 112 is a positive electrode tab portion, and 113 is a positive electrode active layer;
120 is a negative electrode base layer, 121 is a negative electrode base portion, 122 is a negative electrode tab portion, and 123 is a negative electrode active layer;
131 is an inner layer jelly roll membrane, 132 is an outer layer jelly roll membrane;
reference electrode base layer 21, reference electrode lithium layer 22, and reference electrode separator 23;
31 is a positive electrode tab, 32 is a negative electrode tab, and 33 is a reference electrode tab;
41 is a positive electrode terminal, 42 is a negative electrode terminal, and 43 is a reference electrode terminal;
51 is a sleeve shell, 52 is a positive end cover, 531 is a positive insulating plate, and 532 is a negative insulating plate;
and 900 is a cell.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Structure of lithium ion battery with reference electrode
As shown in fig. 1, 2, 3, and 4, the lithium ion battery with a reference electrode includes a case, and a battery cell 900 and an electrolyte disposed in the case. The cell 900 disposed within the housing is wetted by the electrolyte within the housing. The battery cell 900 includes a winding core 100, a reference pole piece 200, and a reference pole diaphragm 23. The winding core 100 is a winding core structure of a lithium ion battery in the prior art, and may be formed by winding a positive electrode tab 11, a winding core diaphragm, and a negative electrode tab 12, for example, refer to fig. 1, 2, and 3; the positive electrode tab 11, the winding core separator, and the negative electrode tab 12 may be stacked, for example, see fig. 4.
In fig. 1, 2 and 3, the core membrane is divided into an inner core membrane 131 and an outer core membrane 132. The winding core 100 is formed by sequentially laminating an outer layer winding core separator 132, a negative electrode tab 12, an inner layer winding core separator 131, and a positive electrode tab 11 and then winding the laminated sheets with the positive electrode tab 11 as an inner side, and may be wound in a circular shape, see fig. 1 and 3, or a flat shape, see fig. 3. In the winding core 100 thus wound, the outermost layer is always the negative electrode tab 12 covered with the outer layer winding core separator 132.
In fig. 4, the winding core 100 is composed of a positive electrode tab 11, a winding core separator 13, and a negative electrode tab 12. The positive electrode plate 11 and the negative electrode plate 12 are arranged alternately, and the positive electrode plate 11 and the negative electrode plate 12 are separated by a winding core diaphragm 13, referring to the enlargement of two circles on the right side of fig. 4, the uppermost layer is the negative electrode plate 12 coated by the winding core diaphragm 13, the lowermost layer is the negative electrode plate 12 coated by the winding core diaphragm 13, that is, the outermost layer is the negative electrode plate 12 coated by the winding core diaphragm 13.
The positive electrode tab 11, referring to fig. 5, includes a positive electrode base layer 110 and a positive electrode active layer 113. The positive electrode base layer 110 is made of a conductive material, and is usually made of a metal material, preferably aluminum or copper, and the thickness is generally 5 to 15 μm. The positive electrode base layer 110 is divided into a positive electrode base portion 111 and a positive electrode tab portion 112. The positive electrode base part 111 has positive electrode active layers 113 coated on both sides thereof, and the positive electrode tab part 112 is a part not coated with the positive electrode active layers 113. The positive electrode tab 112 is used to connect the positive electrode tab 31. The positive electrode tab 112 and the positive electrode tab 31 are connected by welding. The positive active layer 113 can be made of nickel cobalt lithium manganate or lithium iron phosphate or other positive active materials of lithium ion batteries, and is coated on the positive base part 111 according to 0.5-2.0 mol per square meter, and the thickness is 100-200 micrometers.
The negative electrode tab 12, referring to fig. 6, includes a negative electrode base layer 120 and a negative electrode active layer 123. The negative electrode substrate layer 120 is made of a conductive material, and is usually made of a metal material, preferably aluminum or copper, and the thickness is generally 5 to 15 μm. The negative electrode base layer 120 is divided into a negative electrode base portion 121 and a negative electrode ear portion 122. The negative electrode base part 121 is coated with the negative electrode active layer 123 on both sides, and the negative electrode tab part 122 is a part not coated with the negative electrode active layer 123. The negative electrode tab portion 122 is used to connect the negative electrode tab 32. The negative electrode tab portion 122 is connected to the negative electrode tab 32 by welding. The negative electrode active layer 123 is usually formed by coating graphite on the negative electrode base part 121 at a ratio of 4 to 12.5 mol per square meter, and has a thickness of 50 to 150 μm. The negative active layer 123 serves as an anode material layer of the lithium ion battery, and those skilled in the art understand that other negative active materials of the lithium ion battery, such as carbon nanomaterials, silicon-based negative materials, tin alloys, lithium titanate, and tin oxides, may also be used.
The winding core 100 is connected with a positive pole tab 31 and a negative pole tab 32, specifically, the positive pole tab 31 is connected with the positive pole piece 11; the negative electrode tab 32 is connected to the negative electrode tab 12, and more specifically, the positive electrode tab 31 and the negative electrode tab 32 are connected to the positive electrode tab 112 of the positive electrode tab 11 and the negative electrode tab 122 of the negative electrode tab 12. The positive electrode tab 31 and the negative electrode tab 32 may have any shape. For example, in the winding core 100 wound in a circular shape shown in fig. 1 and 2, the positive electrode tab 31 is a cylindrical body located at the center of the circular winding core 100. The winding core 100 is wound around the cylindrical positive electrode tab 31. For another example, in the winding core 100 having the laminated structure shown in fig. 4, each positive electrode tab 11 is connected to a positive electrode tab 112, and the positive electrode tabs 112 of the positive electrode tabs 11 of each layer are welded to each other to form a positive electrode tab 31; the negative electrode tab 32 is formed by welding the negative electrode tab portions 122 of the respective layers of negative electrode tabs 12 to each other.
The reference pole piece 200 is attached to the winding core 100, and includes a reference pole base layer 21 and a reference pole lithium layer 22 attached to the reference pole base layer 21, as shown in fig. 1, 3, and 4. The reference electrode base layer 21 is made of a conductive material, usually a metal material, preferably aluminum or copper, and has a thickness of 4.5 to 30 μm. The reference electrode lithium layer 22 is a lithium metal, typically a lithium film having a thickness of 10 to 30 μm. When the reference electrode sheet 200 is attached to the winding core 100, the reference electrode lithium layer 22 faces inward, and the reference electrode base layer 21 is located outward, so that the reference electrode lithium layer 22 and the negative electrode sheet 12 are separated by the winding core separator. In the example of fig. 1 and 3, the reference lithium electrode layer 22 and the negative electrode tab 12 are separated by an outer layer jellyroll separator 132; in the example of fig. 4, the reference lithium electrode layer 22 and the negative electrode tab 12 are separated by the outermost jellyroll separator 13. In addition, a reference electrode diaphragm 23 is attached to the reference electrode sheet 200. In the example of fig. 1, the winding core 100 has a cylindrical structure, and the reference pole piece 200 and the reference pole separator 23 are attached to the cylindrical surface of the winding core 100 having the cylindrical structure. In the example of fig. 2 and 4, the reference pole piece 200 and the reference pole separator 23 are on one side of the jellyroll 100.
In addition, in general, the reference electrode lithium layer 22 is smaller in size than the reference electrode base layer 21, and the reference electrode lithium layer 22 is located at the center of the reference electrode base layer 21; the reference electrode base layer 21 is smaller in size than the reference electrode separator 23, and the reference electrode base layer 21 is located at the center position of the reference electrode separator 23, so that the entire reference electrode lithium layer 22 is covered by the reference electrode base layer 21, and the entire reference electrode base layer 21 is covered by the reference electrode separator 23. The reference electrode lithium layer 22 is connected to a reference electrode tab 33 via the reference electrode base layer 21. Specifically, the reference electrode tab 33 is connected to the reference electrode base layer 21. The connection between the reference electrode tab 33 and the reference electrode base layer 21 is typically welding.
The cell 900 is entirely disposed in a closed container and is soaked by the electrolyte disposed in the closed container. Referring to fig. 2, fig. 2 shows an example of a lithium ion battery having a cylindrical structure. In the example of fig. 2, the winding core 100 is formed by sequentially stacking an outer winding core diaphragm 132, a negative electrode tab 12, an inner winding core diaphragm 131, and a positive electrode tab 11, and winding the stacked layers around a cylindrical positive electrode tab 31, and has a cylindrical structure. The reference pole piece 200 and the reference pole diaphragm 23 are attached to the cylindrical surface of the winding core 100 having a cylindrical structure to form the battery cell 900 having a cylindrical structure, and the reference pole piece 200 is coated between the cylindrical surface of the winding core 100 and the reference pole diaphragm 23. The axis of the battery core 900 with a cylindrical structure is a positive electrode tab 31. The battery core 900 with a cylindrical structure is arranged in the sleeve shell 51, the top end of the battery core is sealed by the anode end cover 52, and the bottom end of the battery core is sealed by the cathode pole 42. The positive electrode end cap 52 is provided with a positive electrode post 41 at the center and a reference electrode post 43 at the edge. A positive insulating plate 531 is disposed between the positive end cap 52 and the cell 900. A negative insulating plate 532 is disposed between the negative electrode post 42 and the battery cell 900. The positive electrode tab 31 and the reference electrode tab 33 on the battery cell 900 are respectively connected with the positive electrode post 41 and the reference electrode post 43 on the positive electrode end cover 52 after penetrating through the positive electrode insulating plate 531, and the negative electrode tab 32 is connected with the negative electrode post 42 after penetrating through the negative electrode insulating plate 532. In the example of fig. 2, the sleeve housing 51 and the positive end cap 52 constitute the housing of the aforementioned lithium ion battery with reference electrode.
Preparation method of lithium ion battery with reference electrode
The preparation method of the lithium ion battery with the reference electrode comprises the steps of preparing a winding core, preparing a battery core and assembling, injecting and sealing. Wherein the step of preparing a winding core is for preparing a winding core 100; preparing a battery cell, namely preparing a reference pole piece 200 and attaching the reference pole piece 200 to the winding core 100 to form a battery cell 900; the assembly injection sealing step is to seal the prepared battery cell 900 and the electrolyte in the case. According to the foregoing, the structure of the winding core 100 is the same as that of the winding core 100 of the conventional lithium ion battery, and therefore, the specific preparation method thereof is not described in detail herein. The step of liquid injection sealing is the same as the process of liquid injection sealing in the assembly of the conventional lithium ion battery roll core, and the description is omitted herein. The preparation method of the battery cell comprises the following steps:
step S21: rolling a lithium belt with the thickness of 100 microns on a release film into a lithium film with the thickness of 10-30 microns to obtain a laminated sheet of the release film and the lithium film;
step S22: stacking the laminated sheet of the release film and the lithium film on a copper foil with the thickness of 4.5-30 micrometers, and applying a pressure of 8.0-10.0 kilopascals to transfer the lithium film on the laminated sheet of the release film and the lithium film to the copper foil to obtain a reference pole piece formed by stacking the lithium film and the copper foil;
step S23: welding a reference pole lug on a copper foil of a reference pole piece formed by overlapping the lithium film and the copper foil;
step S24: and attaching a reference pole piece formed by overlapping the lithium film and the copper foil to the surface of the winding core in a manner that the lithium film faces the inner side, so that the lithium film and the negative pole piece of the winding core are separated by the winding core diaphragm and are covered by the reference pole diaphragm, and thus the battery core consisting of the winding core and the reference pole piece is obtained.
Third, test data and technical effects
Example 1
In this embodiment, the winding core 100 has a laminated structure shown in fig. 4. Wherein the content of the first and second substances,
1. the parameters of the winding core 100 are as follows:
in the positive electrode sheet 11, an aluminum foil 13 μm thick is used as the positive electrode base layer 111. The positive electrode active layer 112 is made of nickel cobalt lithium manganate. The nickel cobalt lithium manganate is coated on the positive electrode substrate layer 111 according to the single-side coating amount of 162 micrograms per square millimeter to form the positive electrode active layer 112. The dimensions of the positive electrode base layer 111 were 53 mm × 108 mm. The positive electrode tab 31 is an aluminum tab.
In the negative electrode tab 12, a copper foil 8 μm thick is used as the negative electrode base layer 121. The negative electrode active layer 122 uses graphite. The graphite was coated on the negative electrode substrate layer 121 at a single-side coating amount of 103 micrograms per square millimeter to form a negative electrode active layer 122. The negative electrode base layer 121 has dimensions of 55 mm × 110 mm. The negative electrode tab 32 is a copper nickel-plated tab.
The roll core diaphragm 13 is a commercial polypropylene microporous diaphragm with the thickness of 16 microns and the porosity of 50%.
And a winding core 100 with the thickness of about 3.9 mm is obtained after laminating 16 layers of the positive pole piece 11, 17 layers of the negative pole piece 12 and 34 layers of the winding core diaphragm 13.
2. The parameters of the reference pole piece 200 are prepared as follows:
firstly, a 100-micron-thick lithium tape is rolled on a release film, and the thickness of the rolled lithium tape is 20 microns and 6.5 micrograms per square millimeter. After aligning the lithium film rolled on the release film with the copper foil with the thickness of 8 microns, transferring the lithium film to the surface of the copper foil under the pressure of 8.0-10.0 kilopascals, and obtaining a reference electrode substrate layer 21 made of copper material with the thickness of 8 microns and a reference electrode lithium layer 22 made of metal lithium material with the thickness of 20 microns, which are laminated to form the reference electrode sheet 200. Then, a nickel copper plating was welded to the copper foil as a reference electrode tab 33. Wherein the content of the first and second substances,
the reference pole base layer 21 has dimensions of 48 mm × 90 mm;
the dimensions of the reference lithium layer 22 were 40 mm x 70 mm.
The reference electrode separator 23 is made of the same material as the winding core separator 13 and has the following dimensions: 55 mm by 110 mm.
3. The electrolyte adopts commercial electrolyte, the solvent is a mixed solvent formed by mixing ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, and the electrolyte lithium salt is lithium hexafluorophosphate with the concentration of 1 mol per liter.
And (3) attaching the reference pole piece 200 to the winding core 100, and then flexibly wrapping the electrolyte by an aluminum plastic film to obtain the lithium ion battery.
The dimensions of the obtained lithium ion battery were: 4.0 mm × 60 mm × 150 mm.
The capacity of the lithium ion battery obtained was 3.2 hours ampere. When full charge, the voltage difference between the positive and negative electrodes is 4.2V. The resistance between the positive and reference electrodes was 14.7 milliohms; the resistance between the negative electrode and the reference electrode was 9.9 milliohms.
When the new lithium ion battery is charged by 0%, 20%, 40%, 60%, 80% and 100%, the voltage difference between the positive electrode and the negative electrode is respectively as follows: 2.8 volts, 3.55 volts, 3.65 volts, 3.83 volts, 4.01 volts, 4.20 volts, and the voltage difference between the positive electrode and the reference electrode is: 3.25 volts, 3.68 volts, 3.77 volts, 3.92 volts, 4.09 volts, 4.25 volts, the voltages of the negative electrode with respect to the reference electrode were: 0.45 volts, 0.14 volts, 0.13 volts, 0.09 volts, 0.05 volts.
The lithium ion battery was subjected to a cycle sufficiency electrical test. After the charge and discharge are cycled for 500 times, 1000 times, 1500 times, 2000 times and 2500 times, the voltage difference of the positive electrode relative to the reference electrode is respectively as follows: 4.250 volts, 4.244 volts, 4.232 volts, 4.221 volts, 4.192 volts, and the negative relative to the reference voltages are: 0.052 volts, 0.050 volts, 0.044 volts, 0.032 volts, 0.021 volts, -0.008 volts, and the resistance impedance between the positive electrode and the reference electrode is respectively: 16.1 milli-ohms, 17.2 milli-ohms, 18.8 milli-ohms, 19.6 milli-ohms, 22.8 milli-ohms. The resistance impedances between the negative electrode and the reference electrode were 10.3 milliohms, 11.7 milliohms, 13.3 milliohms, 14.6 milliohms, and 16.3 milliohms, respectively.
That is, after 2500 cycles of charging, when the lithium ion battery is fully charged, the voltage difference between the negative electrode and the reference electrode is less than 0, the resistance between the positive electrode and the reference electrode is increased by 55.1% from the initial 14.7 milliohms, and the resistance between the negative electrode and the reference electrode is increased by 64.6% from the initial 9.9 milliohms. And then, disassembling the lithium ion battery, and finding that lithium precipitation is found on the whole surface of the negative pole piece.
Example 2
In this embodiment, the winding core 100 has a flat winding structure shown in fig. 3. Wherein the content of the first and second substances,
1. the parameters of the winding core 100 are as follows:
in the positive electrode sheet 11, an aluminum foil 10 μm thick is used as the positive electrode base layer 111. The positive electrode active layer 112 uses lithium iron phosphate. The lithium iron phosphate was coated on the positive electrode substrate layer 111 at a single-side coating amount of 182 micrograms per square millimeter to form the positive electrode active layer 112. The dimensions of the positive electrode base layer 111 were 14000 mm × 94 mm. The positive electrode tab 31 is an aluminum tab.
In the negative electrode tab 12, a 6 μm thick copper foil is used as the negative electrode base layer 121. The negative electrode active layer 122 uses graphite. The graphite was coated on the negative electrode substrate layer 121 at a single-side coating amount of 103 micrograms per square millimeter to form a negative electrode active layer 122. The negative electrode base layer 121 has dimensions of 14500 mm × 98 mm. The negative electrode tab 32 is a copper nickel-plated tab.
The inner layer roll core membrane 131 and the outer layer roll core membrane 132 both adopt commercial polypropylene microporous membranes, the thickness is 16 microns, and the porosity is 50%.
The dimensions of the wound core 100 are: 40 mm × 215 mm × 103 mm.
2. The parameters of the reference pole piece 200 are prepared as follows:
firstly, a 100-micron-thick lithium tape is rolled on a release film, and the thickness of the rolled lithium tape is 20 microns and 6.5 micrograms per square millimeter. After aligning the lithium film rolled on the release film with the copper foil with the thickness of 8 microns, transferring the lithium film to the surface of the copper foil under the pressure of 8.0-10.0 kilopascals, and obtaining a reference electrode substrate layer 21 made of copper material with the thickness of 8 microns and a reference electrode lithium layer 22 made of metal lithium material with the thickness of 20 microns, which are laminated to form the reference electrode sheet 200. Then, a nickel copper plating was welded to the copper foil as a reference electrode tab 33. Wherein the content of the first and second substances,
the reference pole base layer 21 has a size of 180 mm × 90 mm;
the dimensions of the reference lithium layer 22 were 160 mm x 60 mm.
The reference electrode separator 23 is made of the same material as the roll core separator, and has the following dimensions: 200 mm x 100 mm.
3. The electrolyte adopts commercial electrolyte, the solvent is a mixed solvent formed by mixing ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, and the electrolyte lithium salt is lithium hexafluorophosphate with the concentration of 1 mol per liter.
The reference electrode sheet 200 is attached to the winding core 100 and sealed in a corresponding aluminum case together with an electrolyte to obtain a lithium ion battery.
The size of the lithium ion battery is as follows: 44 mm by 220 mm by 110 mm.
The resulting lithium ion battery had a capacity of 110 hours amps. At full charge, the voltage difference between the positive and negative electrodes was 3.65 volts.
When the new lithium ion battery is charged by 0%, 20%, 40%, 60%, 80% and 100%, the voltage difference between the positive electrode and the negative electrode is respectively as follows: 2.00 volts, 3.03 volts, 3.15 volts, 3.18 volts, 3.21 volts, 3.65 volts, the voltage difference of the positive electrode with respect to the reference electrode is: 2.37 volts, 3.30 volts, 3.35 volts, 3.36 volts, 3.37 volts, 3.69 volts, the voltages of the negative electrode with respect to the reference electrode were: 0.37 volts, 0.27 volts, 0.21 volts, 0.18 volts, 0.16 volts, 0.04 volts.
The lithium ion battery was subjected to a cycle sufficiency electrical test. After the charge and discharge cycles of 2000 times, 4000 times, 5000 times and 5600 times, the voltage difference of the positive electrode relative to the reference electrode at full charge is respectively as follows: 3.690 volts, 3.676 volts, 3.658 volts, 3.646 volts, the voltages of the negative electrode with respect to the reference electrode were: 0.040 volt, 0.026 volt, 0.008 volt, -0.004 volt.
That is, after the full charge is made for 5600 cycles, the voltage difference between the negative electrode and the reference electrode is less than 0. And then, disassembling the lithium ion battery, and finding that lithium precipitation exists on the surface of the negative pole piece.
Example 3
In this embodiment, the winding core 100 has a circular winding structure shown in fig. 1. Wherein the content of the first and second substances,
1. the parameters of the winding core 100 are as follows:
in the positive electrode sheet 11, an aluminum foil 10 μm thick is used as the positive electrode base layer 111. The positive electrode active layer 112 is made of nickel cobalt lithium manganate. The nickel cobalt lithium manganate is coated on the positive electrode substrate layer 111 according to the single-side coating amount of 165 micrograms per square millimeter to form the positive electrode active layer 112. The dimensions of the positive electrode base layer 111 were 820 mm × 55 mm. The positive electrode tab 31 is an aluminum tab.
In the negative electrode tab 12, a 6 μm thick copper foil is used as the negative electrode base layer 121. The negative electrode active layer 122 uses graphite. The graphite was coated on the negative electrode substrate layer 121 at a single-side coating amount of 103 micrograms per square millimeter to form a negative electrode active layer 122. The negative electrode base layer 121 has a size of 880 mm × 57 mm. The negative electrode tab 32 is a copper nickel-plated tab.
The inner layer roll core membrane 131 and the outer layer roll core membrane 132 both adopt commercial polypropylene microporous membranes, the thickness is 16 microns, and the porosity is 50%.
The dimensions of the wound core 100 are: diameter 17.3 mm and height 59.5 mm.
2. The parameters of the reference pole piece 200 are prepared as follows:
firstly, a 100-micron-thick lithium tape is rolled on a release film, and the thickness of the rolled lithium tape is 20 microns and 6.5 micrograms per square millimeter. After aligning the lithium film rolled on the release film with the copper foil with the thickness of 8 microns, transferring the lithium film to the surface of the copper foil under the pressure of 8.0-10.0 kilopascals, and obtaining a reference electrode substrate layer 21 made of copper material with the thickness of 8 microns and a reference electrode lithium layer 22 made of metal lithium material with the thickness of 20 microns, which are laminated to form the reference electrode sheet 200. Then, a nickel copper plating was welded to the copper foil as a reference electrode tab 33. Wherein the content of the first and second substances,
the reference pole base layer 21 has dimensions of 50 mm × 50 mm;
the dimensions of the reference lithium layer 22 were 40 mm x 40 mm.
The reference electrode separator 23 is made of the same material as the roll core separator, and has the following dimensions: 60 mm x 56 mm.
3. The electrolyte adopts commercial electrolyte, the solvent is a mixed solvent formed by mixing ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, and the electrolyte lithium salt is lithium hexafluorophosphate with the concentration of 1 mol per liter.
The reference electrode sheet 200 is attached to the winding core 100, and sealed with an electrolyte in a steel sleeve case 51, and sealed with a positive end cap 52 to obtain a lithium ion battery.
The size of the lithium ion battery is as follows: 18.0 mm in diameter and 65.0 mm in height.
The capacity of the lithium ion battery obtained was 3.4 hours ampere. At full charge, the voltage difference between the positive and negative electrodes was 4.25 volts.
When the new lithium ion battery is charged by 0%, 20%, 40%, 60%, 80% and 100%, the voltage difference between the positive electrode and the negative electrode is respectively as follows: 2.80 volts, 3.60 volts, 3.70 volts, 3.88 volts, 4.06 volts, 4.25 volts, and the voltage difference between the positive electrode and the reference electrode are: 3.30 volts, 3.73 volts, 3.82 volts, 3.97 volts, 4.14 volts, 3.30 volts, the voltages of the negative electrode with respect to the reference electrode were: 0.50 volt, 0.13 volt, 0.12 volt, 0.09 volt, 0.08 volt, 0.05 volt.
The lithium ion battery was subjected to a cycle sufficiency electrical test. After the charge and discharge are cycled for 500 times, 1000 times, 1200 times, 1500 times and 1800 times, the voltage difference of the positive electrode relative to the reference electrode at full charge is respectively as follows: 4.300V, 4.290V, 4.275V, 4.254V and 4.240V, wherein the voltages of the negative electrode relative to the reference electrode are respectively as follows: 0.060 volts, 0.050 volts, 0.040 volts, 0.025 volts, -0.012 volts.
Namely, after the lithium ion battery is fully charged after being circulated for 1800 times, the voltage difference of the negative electrode relative to the reference electrode is less than 0. And then, disassembling the lithium ion battery, and finding that lithium precipitation exists on the surface of the negative pole piece.
Fourth, supplementary explanation
With respect to the size of the reference-electrode lithium layer, it was found through experiments that if the reference-electrode lithium layer is too small, the voltage of the negative electrode to the reference electrode was detected to be unstable. In particular, according to the three embodiments, when the lithium ion battery is fully charged, the maximum voltage of the negative electrode to the reference electrode is not more than 50 mv, and if the size of the lithium layer of the reference electrode is too small, the detected error is relatively large. Thus, in general, the larger the reference lithium layer, the better. Preferably, in the case of the cylindrical winding core 100 of fig. 1, the area of the reference lithium electrode layer is half of the area of the cylindrical surface of the cylinder, and in the case of the winding core 100 of the square structure of fig. 3 and 4, the area of the reference lithium electrode layer exceeds half of the area of the side surface thereof.
Claims (10)
1. The lithium ion battery with the reference electrode comprises a shell and a winding core arranged in the shell; the winding core is formed by laminating or winding a positive pole piece, a winding core diaphragm and a negative pole piece; the positive pole piece and the negative pole piece are respectively connected with a positive pole post and a negative pole post which are arranged on the shell through a positive pole lug and a negative pole lug; the device is characterized by also comprising a reference pole piece arranged in the shell; the reference pole piece comprises a reference pole lithium layer; the outermost layer of the winding core is the negative pole piece coated by the winding core diaphragm; the reference pole piece is tightly attached to the winding core, so that the reference pole lithium layer is separated from the negative pole piece through the winding core diaphragm, and the reference pole piece is coated by the reference pole diaphragm; the reference pole lithium layer is connected with a reference pole lug and is connected with a reference pole arranged on the shell through the reference pole lug, and the reference pole lithium layer is made of metal lithium.
2. The lithium ion battery with a reference electrode according to claim 1, wherein the reference electrode lithium layer is a lithium film having a thickness of 10 to 30 μm and an area of not less than 1 cm.
3. The lithium ion battery of claim 1, wherein the reference pole piece further comprises a reference pole base layer; the reference electrode substrate layer is made of a conductive material; the reference electrode lithium layer is disposed on the reference electrode base layer; the reference pole base layer is connected with the reference pole tab.
4. The reference-pole lithium ion battery of claim 3, wherein the reference-pole lithium layer is smaller in size than the reference-pole base layer, which is smaller than the reference-pole separator membrane, such that the reference-pole lithium layer is encapsulated by the reference-pole base layer, which is encapsulated by the reference-pole separator membrane.
5. The lithium ion battery of claim 3, wherein the reference electrode base layer is made of copper foil.
6. The lithium ion battery of claim 1 or 2 or 3 or 4 or 5 with a reference electrode, wherein the jellyroll separator comprises an outer jellyroll separator and an inner jellyroll separator; the winding core is formed by sequentially laminating and winding an outer layer winding core diaphragm, a negative pole piece, an inner layer winding core diaphragm and a positive pole piece; the reference electrode lithium layer is separated from the negative electrode pole piece through the outer layer coiled core diaphragm.
7. The lithium ion battery with the reference electrode according to claim 1, 2, 3, 4 or 5, wherein the winding core is formed by alternately laminating a positive electrode sheet and a negative electrode sheet; the positive pole piece and the negative pole piece are separated by the winding core diaphragm.
8. The lithium ion battery with reference electrode according to claim 1, 2, 3, 4 or 5, wherein the positive electrode sheet comprises a positive electrode substrate layer and a positive electrode active layer disposed on the positive electrode substrate layer; the positive electrode active layer is made of active lithium; the negative pole piece comprises a negative pole substrate layer and a negative pole active layer arranged on the negative pole substrate layer.
9. The lithium ion battery with reference electrode of claim 8, wherein the active lithium is nickel cobalt lithium manganate or lithium iron phosphate.
10. A method for manufacturing a lithium ion battery with a reference electrode, characterized in that the method for manufacturing a lithium ion battery with a reference electrode according to claim 3 comprises a step of manufacturing a winding core, a step of manufacturing a battery cell, and a step of assembling, injecting and sealing; the step of preparing the winding core is used for preparing the winding core;
wherein the step of preparing the battery cell comprises:
step S21: rolling a lithium belt with the thickness of 100 microns on a release film into a lithium film with the thickness of 10-30 microns to obtain a laminated sheet of the release film and the lithium film;
step S22: stacking the laminated sheet of the release film and the lithium film on a copper foil with the thickness of 4.5-30 micrometers, and applying a pressure of 8.0-10.0 kilopascals to transfer the lithium film on the laminated sheet of the release film and the lithium film to the copper foil to obtain a reference pole piece formed by stacking the lithium film and the copper foil;
step S23: welding a reference pole lug on a copper foil of a reference pole piece formed by overlapping the lithium film and the copper foil;
step S24: attaching a reference pole piece formed by overlapping the lithium film and the copper foil to the surface of the winding core in a manner that the lithium film faces the inner side, so that the lithium film is separated from a negative pole piece of the winding core through a winding core diaphragm and is covered by the reference pole diaphragm, and thus obtaining an electric core consisting of the winding core and the reference pole piece;
and the step of assembling, injecting and sealing is used for packaging the prepared battery core and the electrolyte into the shell.
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