WO2024239459A1 - 组合电芯及应用其的电池 - Google Patents

组合电芯及应用其的电池 Download PDF

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Publication number
WO2024239459A1
WO2024239459A1 PCT/CN2023/112087 CN2023112087W WO2024239459A1 WO 2024239459 A1 WO2024239459 A1 WO 2024239459A1 CN 2023112087 W CN2023112087 W CN 2023112087W WO 2024239459 A1 WO2024239459 A1 WO 2024239459A1
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Prior art keywords
positive electrode
ion battery
battery
negative electrode
lithium
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Ceased
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PCT/CN2023/112087
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English (en)
French (fr)
Inventor
刘航
王超
胡骐
曾汉民
何巍
刘金成
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Eve Power Co Ltd
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Eve Power Co Ltd
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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
    • H01M10/058—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
    • H01M10/052—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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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

Definitions

  • the present application belongs to the field of battery technology, and specifically, relates to a combined battery cell and a battery using the same.
  • Lithium-ion batteries have high energy density, but the cost of raw materials continues to grow.
  • Sodium-ion batteries have stable electrochemical performance, significant cost and safety advantages, but low energy density and short cycle life. How to effectively leverage the complementary advantages of sodium-ion batteries and lithium-ion batteries has always been a difficult problem in the industry.
  • the industry generally uses battery PACK to combine batteries with different cells, but differences in battery life aging patterns and SOC-OCV differences require precise control and management of BMS technology, and the commonly used CMP (Cell-Module-Pack) three-level architecture has low space utilization and low energy density.
  • CMP Cell-Module-Pack
  • the present application provides a combined battery cell and a battery using the same, so that the same battery cell can have the performance advantages of both lithium-ion batteries and sodium-ion batteries, thereby further improving the energy density and cycle performance of the battery.
  • a combined battery cell comprises a positive electrode sheet, a negative electrode sheet and a separator, the positive electrode sheet comprises at least two of a sodium ion battery positive electrode sheet, a lithium ion battery positive electrode sheet and a composite positive electrode sheet, the negative electrode sheet comprises at least two of a sodium ion battery negative electrode sheet, a lithium ion battery negative electrode sheet and a composite negative electrode sheet;
  • the positive electrode active coating of the sodium ion battery positive electrode sheet contains a first positive electrode active material suitable for sodium ion batteries;
  • the positive electrode active coating of the lithium ion battery positive electrode sheet contains a second positive electrode active material suitable for lithium ion batteries;
  • the composite positive electrode sheet comprises a sodium ion battery positive electrode active coating and a lithium ion battery positive electrode active coating respectively arranged on two back-to-back sides of a current collector, the sodium ion battery positive electrode active coating contains a third positive electrode active material suitable for sodium ion batteries, and the lithium ion
  • a battery comprising the above-mentioned combined battery cell, the battery being a lithium ion battery, a sodium ion battery or a potassium ion battery.
  • the battery provided in the present application has both good energy density and cycle performance.
  • the lithium-ion battery type positive electrode active material and the sodium-ion battery type positive electrode active material are respectively made into lithium-ion battery positive electrode sheets and sodium-ion battery positive electrode sheets, or the positive electrode active coatings formed by the lithium-ion battery type positive electrode active material and the sodium-ion battery type positive electrode active material are respectively arranged on both sides of the current collector to form a composite positive electrode sheet, which directly avoids the above problems.
  • the combined battery cell provided in the present application can give full play to the synergistic performance advantages of lithium-ion batteries and sodium-ion batteries, and has the characteristics of high energy density and good cycle performance.
  • FIG1 is a schematic structural diagram of a combined battery cell 1 prepared in Example 2;
  • FIG2 is a schematic diagram of the structure of the combined battery cell 2 prepared in Example 2;
  • FIG. 3 is a schematic structural diagram of a combined battery cell 7 prepared in Example 3.
  • the combined battery cell includes at least two of the following electrode units: a sodium ion electrode unit A, a lithium ion electrode unit B, a sodium ion-lithium ion combination electrode unit C, and a sodium ion-lithium ion combination electrode unit D;
  • the sodium ion electrode unit A includes a sodium ion battery positive electrode sheet, a diaphragm, and a sodium ion battery negative electrode sheet;
  • the lithium ion electrode unit B includes a lithium ion battery positive electrode sheet, a diaphragm, and a lithium ion battery negative electrode sheet;
  • the sodium ion-lithium ion combination electrode unit C includes a composite positive electrode sheet, a diaphragm, a sodium ion battery negative electrode sheet, and a lithium ion battery negative electrode sheet.
  • the sodium ion-lithium ion combined electrode plate unit D includes a sodium ion battery positive electrode plate, a lithium i
  • a sodium ion pole piece unit A by setting up and constructing a sodium ion pole piece unit A, a lithium ion pole piece unit B, a sodium ion-lithium ion combination pole piece unit C, and a sodium ion-lithium ion combination pole piece unit D, different positive pole pieces containing positive electrode active materials suitable for sodium ion batteries and positive electrode active materials suitable for lithium ion batteries can be matched with suitable negative pole pieces, so that conductive particles can be smoothly transmitted between different types of positive pole pieces.
  • the combined battery cell includes at least a sodium ion pole piece unit A, a lithium ion pole piece unit B and a connecting pole piece unit.
  • the sodium ion pole piece unit A and the lithium ion pole piece unit B are connected by the connecting pole piece unit.
  • the connecting pole piece unit is selected from at least one of the sodium ion-lithium ion combined pole piece unit C and the sodium ion-lithium ion combined pole piece unit D.
  • the first positive electrode active material and the third positive electrode active material independently include at least one of a transition metal oxide positive electrode material, a polyanion positive electrode material, a Prussian blue compound positive electrode material, and a Prussian white compound positive electrode material suitable for a sodium ion battery;
  • the second positive electrode active material and the fourth positive electrode active material independently include at least one of a phosphate positive electrode material and a lithium oxide-containing material suitable for a lithium ion battery;
  • the first negative electrode active material includes at least one of a hard carbon, a soft carbon, an alloy-type negative electrode active material, and a titanium-based negative electrode active material suitable for a sodium ion battery;
  • the second negative electrode active material includes at least one of artificial graphite, natural graphite, a silicon negative electrode, hard carbon, and soft carbon suitable for a lithium ion battery.
  • the first positive electrode active material and the third positive electrode active material independently include transition metal oxide positive electrode materials
  • the second positive electrode active material and the fourth positive electrode active material independently include phosphate positive electrode materials.
  • the resulting combined battery cell has good stability, and in the process of application, by simultaneously charging and discharging the phosphate positive electrode material (lithium ion battery type positive electrode active material) and the transition metal oxide positive electrode material (sodium ion battery type positive electrode active material), the combined battery cell can exhibit excellent cycle performance.
  • the first positive electrode active material and the third positive electrode active material independently include polyanion positive electrode materials
  • the second positive electrode active material and the fourth positive electrode active material independently include lithium oxide material positive electrode materials.
  • the combined battery cell integrating the above two positive electrode active materials has a higher energy density and good cycle stability.
  • the positive electrode plate of the sodium ion battery comprises a polyanion positive electrode plate
  • the first positive electrode active material contained in the polyanion positive electrode plate is a polyanion positive electrode material (sodium ion battery positive electrode active material)
  • the positive electrode plate of the lithium ion battery comprises a phosphate
  • the second positive electrode active material contained in the phosphate-type positive electrode plate is a phosphate-type positive electrode material (lithium-ion battery type positive electrode active material)
  • the second positive electrode active material contained in the lithium-oxide-containing positive electrode plate is a lithium-oxide-containing positive electrode material (lithium-ion battery type positive electrode active material).
  • the combined battery cell integrating the above three positive electrode active materials has the excellent characteristics of high energy density, high cycle stability and high safety.
  • the average surface density of the positive electrode active coating included therein is S1n
  • the mass content of the first positive electrode active material in the positive electrode sheet of the sodium ion battery containing it is W1n
  • the cumulative capacity per unit area of the positive electrode sheet of the sodium ion battery is
  • i represents the number of positive electrode sheets of the sodium ion battery
  • the average surface density of the positive electrode active coating included therein is S2n
  • the mass content of the second positive electrode active material in the positive electrode sheet of the lithium ion battery containing it is W2n
  • the cumulative capacity per unit area of the positive electrode sheet of the lithium ion battery is
  • k represents the number of lithium-ion battery positive electrode sheets
  • the composite positive electrode sheet the average surface density of the sodium-ion battery positive electrode active coating is S3n
  • i ⁇ 200, k ⁇ 200 In one embodiment, i ⁇ 200, k ⁇ 200.
  • the thickness of the positive electrode sheet of the sodium ion battery is 100-300 ⁇ m
  • the thickness of the positive electrode sheet of the lithium ion battery is 100-400 ⁇ m
  • the thickness of the negative electrode sheet is 100-500 ⁇ m.
  • the positive electrode active material used in the following sodium ion battery positive electrode plate is recorded as the "first positive electrode active material”, and the positive electrode active material used in the following lithium ion battery positive electrode plate is recorded as the "second positive electrode active material”;
  • the positive electrode active material used in the positive electrode active coating of the sodium ion battery in the following composite positive electrode plate is recorded as the "third positive electrode active material”, and the positive electrode material used in the positive electrode active coating of the lithium ion battery in the following composite positive electrode plate is recorded as the "fourth positive electrode active material”;
  • the negative electrode active material used in the negative electrode plate of the following sodium ion battery is recorded as the "first negative electrode active material”;
  • the negative electrode active material used in the negative electrode plate of the following lithium ion battery is recorded as the "second negative electrode active material”;
  • the negative electrode active material used in the negative electrode active coating of the sodium ion battery in the following composite positive electrode plate is recorded as the "third negative electrode active material", and the negative electrode active material used in
  • Layered transition metal oxide NaMnO2 is used as the first positive electrode active material, and NaMnO2 , a binder PVDF, and a conductive agent acetylene black are uniformly combined in a mass ratio of 80:10:10 to form a positive electrode coating slurry, and then the positive electrode coating slurry is respectively coated on two back-to-back sides of a positive electrode current collector, and dried to form symmetrical positive electrode active coatings on two sides of the positive electrode current collector, thereby preparing a sodium-type transition metal oxide positive electrode sheet, wherein the single-side average surface density of the positive electrode active coating included therein is 30-500 g/ m2 .
  • the polyanion compound NASICON is used as the first positive electrode active material, and NASICON, a binder PVDF, and a conductive agent acetylene black are uniformly combined in a mass ratio of 90:5:5 to form a positive electrode coating slurry, and then the positive electrode coating slurry is respectively coated on two back-to-back sides of the positive electrode current collector, and dried to form symmetrical positive electrode active coatings on the two sides of the positive electrode current collector to prepare a sodium-type polyanion positive electrode sheet, wherein the single-side average surface density of the positive electrode active coating included therein is 50-500 g/ m2 .
  • Phosphate LiFePO 4 is used as the second positive electrode active material.
  • LiFePO 4 , binder PVDF, and conductive agent acetylene black are evenly mixed in a mass ratio of 97:2:1 to prepare a positive electrode coating slurry.
  • the positive electrode coating slurry is dried to form symmetrical positive electrode active coatings on two sides of the positive electrode current collector to prepare a lithium battery-phosphate positive electrode sheet, wherein the single-side average surface density of the positive electrode active coating is 80-450 g/m 2 .
  • NCM622 is used as the second positive electrode active material, and NCM622, a binder PVDF, and a conductive agent acetylene black are uniformly combined in a mass ratio of 97:2:1 to prepare a positive electrode coating slurry, and then the positive electrode coating slurry is respectively coated on two back-to-back sides of the positive electrode current collector, and dried, so that symmetrical positive electrode active coatings are formed on the two sides of the positive electrode current collector, and a lithium battery-lithium oxide-containing positive electrode sheet is prepared, wherein the single-side average surface density of the positive electrode active coating included therein is 50-450 g/m 2 .
  • the polyanion compound NASICON is used as the third positive electrode active material
  • NCM622 is used as the fourth positive electrode active material.
  • NASICON, binder PVDF, and conductive agent acetylene black are combined in a mass ratio of 90:5:5 to prepare a first positive electrode coating slurry
  • NCM622, binder PVDF, and conductive agent acetylene black are combined in a mass ratio of 97:2:1 to prepare a second positive electrode coating slurry; then the first positive electrode coating slurry is applied on one side of the positive electrode current collector and dried to form a positive electrode active coating of a sodium ion battery on one side of the positive electrode current collector; then, the second positive electrode coating slurry is applied on the other side of the positive electrode current collector and dried to form a positive electrode active coating of a lithium ion battery on the other side of the positive electrode current collector; and a composite positive electrode sheet is prepared through the above steps.
  • Hard carbon is used as the first negative electrode active material, and the hard carbon, conductive agent acetylene black, binder sodium carboxymethyl cellulose (CMC), and styrene-butadiene rubber (SBR) are combined in a mass ratio of 94:1:2:3 to prepare a negative electrode coating slurry, and then the negative electrode coating slurry is coated on two back-to-back sides of the negative electrode collector respectively, and dried to form symmetrically arranged negative electrode active coatings on the two sides of the negative electrode collector to prepare a negative electrode sheet for a sodium ion battery.
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • Natural graphite is used as the second negative electrode active material, and natural graphite, conductive agent acetylene black, binder sodium carboxymethyl cellulose (CMC), and styrene butadiene rubber (SBR) are combined in a mass ratio of 94:1:2:3 to prepare a negative electrode coating slurry, and then the negative electrode coating slurry is coated on two back-to-back sides of the negative electrode current collector, respectively, and dried, so that a symmetrically arranged negative electrode active coating is formed on the two sides of the negative electrode current collector.
  • a negative electrode sheet for a lithium-ion battery is obtained.
  • Hard carbon is used as the third negative electrode active material, and natural graphite is used as the fourth negative electrode active material.
  • Hard carbon, conductive agent acetylene black, binder sodium carboxymethyl cellulose (CMC), and styrene butadiene rubber (SBR) are combined in a mass ratio of 94:1:2:3 to prepare a first negative electrode coating slurry, and natural graphite, conductive agent acetylene black, binder sodium carboxymethyl cellulose (CMC), and styrene butadiene rubber (SBR) are combined in a mass ratio of 94:1:2:3 to prepare a second negative electrode coating slurry; then the first negative electrode coating slurry is applied on one side of the negative electrode current collector and dried to form a negative electrode active coating of a sodium ion battery on one side of the negative electrode current collector; then, the second negative electrode coating slurry is applied on the other side of the negative electrode current collector and dried to form a negative electrode active coating of a lithium
  • the lithium battery-phosphate type positive electrode sheet, sodium battery-transition metal oxide positive electrode sheet and composite negative electrode sheet, lithium ion battery negative electrode sheet, and sodium ion battery negative electrode sheet prepared in Example 1 are used in different combinations to prepare different combined battery cells, and then the battery is prepared according to the following method: the positive electrode sheet and the negative electrode sheet are arranged in sequence, and each electrode sheet is separated by a diaphragm, and the combined battery cell is prepared by a lamination or winding process; then the combined battery cell is placed in a battery shell, and then the battery shell is subjected to treatments such as welding the pole ears and baking, and after the moisture content is tested to be qualified, an appropriate amount of electrolyte is injected into the battery shell, and the battery is packaged, and the battery is prepared by aging, forming, and exhaust packaging.
  • the separator used is a polyethylene film.
  • the combined battery cell 1 includes 25 lithium battery-phosphate type positive electrode sheets 1-1, 49 composite negative electrode sheets 1-2, 25 sodium battery-transition metal oxide positive electrode sheets 1-3, 1 lithium ion battery negative electrode sheet 1-4, and 1 sodium ion battery negative electrode sheet 1-5.
  • the composite negative electrode sheet 1-2 is arranged between the lithium battery-phosphate type positive electrode sheet 1-1 and the sodium battery-transition metal oxide positive electrode sheet 1-3, and on both sides of the composite negative electrode sheet 1-2, the sodium battery negative electrode active coating 1-22 of the composite negative electrode sheet 1-2 is arranged with the sodium battery-transition metal oxide positive electrode sheet 1-3, and the lithium battery-phosphate type positive electrode sheet 1-1 is arranged toward the lithium battery negative electrode active coating 1-21 of the composite negative electrode sheet 1-2; in the above-mentioned electrode sheet, the lithium battery-phosphate type positive electrode sheet 1-1, the composite negative electrode sheet 1-2, the sodium battery-transition metal oxide positive electrode sheet 1-3, the composite negative electrode sheet 1-2, the lithium battery-phosphate type positive electrode sheet 1-3, the composite negative electrode sheet 1-2, the lithium battery-phosphate type positive electrode sheet The electrode sheets 1-1 are repeatedly arranged in sequence and the separators arranged between the above-mentioned electrode sheets constitute a
  • the combined battery cell 1 includes a sodium ion-lithium ion combination electrode sheet unit D.
  • a lithium ion battery negative electrode sheet 1-4 and a sodium ion battery negative electrode sheet 1-5 are respectively arranged at both ends of the sodium ion-lithium ion combination electrode sheet unit D, wherein the lithium ion battery negative electrode sheet 1-4 is arranged at one end adjacent to the sodium ion-lithium ion combination electrode sheet unit D in which the lithium battery-phosphate type positive electrode sheet 1-1 is arranged, and the sodium ion battery negative electrode sheet 1-5 is arranged at one end adjacent to the sodium ion-lithium ion combination electrode sheet unit D in which the sodium battery-transition metal oxide positive electrode sheet 1-3 is arranged.
  • the combined battery cell 2 includes 25 lithium-phosphate positive electrode sheets 2-1, 1 composite negative electrode sheet 2-2, 25 sodium-transition metal oxide positive electrode sheets 2-3, 25 sodium-ion battery negative electrode sheets 2-5, and 25 lithium-ion battery negative electrode sheets 2-4.
  • 25 sodium-transition metal oxide positive electrode sheets 2-3, 25 sodium-ion battery negative electrode sheets 2-5 are sequentially arranged and the separator 2-6 arranged between the above-mentioned electrodes constitutes a sodium-ion electrode sheet unit A
  • 25 lithium-phosphate positive electrode sheets 2-1, 25 lithium-ion battery negative electrode sheets 2-4 are sequentially arranged and the separator 2-6 arranged between the above-mentioned electrodes constitutes a lithium-ion electrode sheet unit B.
  • the combined battery cell 2 includes one sodium-ion electrode sheet unit A, one lithium-ion electrode sheet unit B, and one sodium-lithium-ion electrode sheet unit D.
  • the above-mentioned The sodium ion pole piece unit A and the lithium ion pole piece unit B are connected by a composite negative electrode piece 2-2.
  • the composite negative electrode piece 2-2 is arranged between the sodium battery-transition metal oxide positive electrode piece 2-3 of the sodium ion pole piece unit A and the lithium battery-phosphate positive electrode piece 2-1 of the lithium ion pole piece unit B.
  • the sodium battery-transition metal oxide positive electrode piece 2-3 is arranged toward the sodium ion battery negative electrode active coating 2-22 of the composite negative electrode piece 2-2, and the lithium battery-phosphate positive electrode piece 2-1 is arranged toward the lithium ion battery negative electrode active coating 2-21 of the composite negative electrode piece 2-2.
  • the sodium ion-lithium ion combined pole piece unit D is formed by sequentially arranging one lithium battery-phosphate positive electrode piece 2-1, one composite negative electrode piece 2-2, and one sodium battery-transition metal oxide positive electrode piece 2-3 at the above connection and a diaphragm arranged between the above pole pieces.
  • the combined battery cell 3 is composed of a lithium-ion electrode unit B, which includes 50 lithium-ion battery-phosphate type positive electrode sheets and 51 lithium-ion battery negative electrode sheets.
  • a lithium-ion electrode unit B which includes 50 lithium-ion battery-phosphate type positive electrode sheets and 51 lithium-ion battery negative electrode sheets.
  • the lithium-ion battery-phosphate type positive electrode sheets and the lithium-ion battery negative electrode sheets are repeatedly arranged in sequence, and a separator is arranged between the lithium-ion battery-phosphate type positive electrode sheets and the lithium-ion battery negative electrode sheets.
  • the combined battery cell 4 is composed of a sodium ion electrode unit A, which includes 50 sodium-type transition metal oxide positive electrode sheets and 51 sodium ion battery negative electrode sheets.
  • a sodium ion electrode unit A which includes 50 sodium-type transition metal oxide positive electrode sheets and 51 sodium ion battery negative electrode sheets.
  • the sodium-type transition metal oxide positive electrode sheets and the sodium ion battery negative electrode sheets are repeatedly arranged in sequence, and a diaphragm is arranged between the sodium-type transition metal oxide positive electrode sheets and the sodium ion battery negative electrode sheets.
  • Example 2 the battery prepared in Example 2 was used as a test object to conduct relevant performance tests.
  • the test battery was charged to 4.25V at 0.33C constant current and constant voltage, cut off at 0.02C, and then discharged to 2.8V at 0.33C.
  • the capacity, average voltage and cell mass were recorded.
  • the battery under test was charged to 4.25V at 0.33C constant current and constant voltage, and then cut off at 0.02C. Then, it was discharged at 0.33C for 90min, left for 10min, and the terminal voltage V1 was recorded. Then, it was discharged at 2C (current I) for 10s, and the terminal voltage V2 was recorded.
  • the tested batteries were placed in a 45°C constant temperature box, charged at 1C constant current and constant voltage, cut off at 0.02C, and then discharged at 1C to 80% SOH, and the number of cycles was recorded.
  • the lithium battery-lithium oxide-containing positive electrode sheet, sodium battery-polyanion positive electrode sheet and composite negative electrode sheet, lithium ion battery negative electrode sheet, and sodium ion battery negative electrode sheet prepared in Example 1 are used in different combinations to prepare different combined battery cells, and then the battery is prepared according to the following method: the positive electrode sheet and the negative electrode sheet are arranged in sequence, and each electrode sheet is separated by a diaphragm, and the combined battery cell is prepared by a stacking or winding process; then the combined battery cell is placed in a battery shell, and then the battery shell is subjected to treatments such as welding the pole ears and baking, and after the moisture content is tested to be qualified, an appropriate amount of electrolyte is injected into the battery shell, and the battery is packaged, and the battery is prepared by aging, forming, and exhaust packaging.
  • the separator used is a polyethylene film.
  • the combined battery cell 5 includes 25 lithium battery-lithium oxide-containing positive electrode sheets, 49 composite negative electrode sheets, 25 sodium battery-polyanion-type positive electrode sheets, 1 lithium ion battery negative electrode sheet, and 1 sodium ion battery negative electrode sheet.
  • the composite negative electrode sheet is arranged between the lithium battery-lithium oxide-containing positive electrode sheet and the sodium battery-polyanion-type positive electrode sheet, and on both sides of the composite negative electrode sheet, the sodium battery-polyanion-type positive electrode sheet is arranged toward the sodium battery negative electrode active coating of the composite negative electrode sheet, and the lithium battery-lithium oxide-containing positive electrode sheet is arranged toward the lithium battery negative electrode active coating of the composite negative electrode sheet; in the above-mentioned electrode sheets, the lithium battery-lithium oxide-containing positive electrode sheet, the composite negative electrode sheet, the sodium battery-polyanion-type positive electrode sheet, and the sodium battery-polyanion-type positive electrode sheet are arranged.
  • the electrode sheet, the composite negative electrode sheet, the lithium battery type-lithium oxide-containing positive electrode sheet are repeatedly arranged in sequence, and the separator arranged between the above-mentioned electrode sheets constitutes a sodium ion-lithium ion combined electrode sheet unit D.
  • the combined battery cell 5 includes a sodium ion-lithium ion combined electrode sheet unit D.
  • a lithium ion battery negative electrode sheet and a sodium ion battery negative electrode sheet are respectively arranged, wherein the lithium ion battery negative electrode sheet is adjacent to the sodium ion-lithium ion combined electrode sheet unit D.
  • One end of a lithium battery-type lithium oxide-containing positive electrode plate is set in the middle, and one end of a sodium battery-type polyanion-type positive electrode plate is set in the sodium ion-lithium ion combination electrode plate unit D adjacent to the sodium ion battery negative electrode plate.
  • the combined battery cell 6 includes 25 lithium battery-type lithium oxide-containing positive electrode sheets, 1 composite negative electrode sheet, 25 sodium battery-type polyanion-type positive electrode sheets, 25 sodium ion battery negative electrode sheets, and 25 lithium ion battery negative electrode sheets.
  • 25 sodium battery-type polyanion-type positive electrode sheets, 25 sodium ion battery negative electrode sheets are arranged in sequence and the separators arranged between the above-mentioned electrodes constitute the sodium ion electrode sheet unit A
  • 25 lithium battery-type lithium oxide-containing positive electrode sheets, 25 lithium ion battery negative electrode sheets are arranged in sequence and the separators arranged between the above-mentioned electrodes constitute the lithium ion electrode sheet unit B.
  • the combined battery cell 1 includes a sodium ion pole piece unit A, a lithium ion pole piece unit B and a lithium ion pole piece unit D.
  • the sodium ion pole piece unit A and the lithium ion pole piece unit B are connected by a composite negative electrode pole piece.
  • the composite negative electrode pole piece is arranged between the sodium battery type-polyanion type positive electrode pole piece of the sodium ion pole piece unit A and the lithium battery type-lithium oxide type positive electrode pole piece of the lithium ion pole piece unit B.
  • the sodium battery type-polyanion type positive electrode pole piece is arranged toward the sodium ion battery negative electrode active coating of the composite negative electrode pole piece
  • the lithium battery type-lithium oxide type positive electrode pole piece is arranged toward the lithium ion battery negative electrode active coating of the composite negative electrode pole piece.
  • the sodium ion-lithium ion combined pole piece unit D is formed by sequentially arranging a lithium battery type-lithium oxide type positive electrode pole piece, a composite negative electrode pole piece, and a sodium battery type-polyanion type positive electrode pole piece at the connection, and a separator arranged between the above pole pieces.
  • the combined battery cell 7 includes 49 composite positive electrode sheets 3-2, 1 lithium battery type - lithium oxide type positive electrode sheet 3-4, 1 sodium battery type - polyanion type positive electrode sheet 3-5, 25 lithium ion battery negative electrode sheets 3-1, and 25 sodium ion battery negative electrode sheets 3-3.
  • the composite positive pole piece 3-2 is arranged between the lithium-ion battery negative pole piece 3-1 and the sodium-ion battery negative pole piece 3-3, and on both sides of the composite positive pole piece 3-2, the sodium-ion battery negative pole piece 3-3 is arranged toward the sodium battery positive active coating 3-22 of the composite positive pole piece 3-2, and the sodium-ion battery negative pole piece 3-3 is arranged toward the lithium battery positive active coating 3-21 of the composite positive pole piece 3-2; in the above-mentioned pole piece, the lithium-ion battery negative pole piece 3-1, the composite positive pole piece 3-2, the sodium-ion battery negative pole piece 3-3, the composite positive pole piece 3-2, and the lithium-ion battery negative pole piece 3-1 are repeatedly arranged in sequence and arranged
  • the diaphragm 3-6 disposed between the above-mentioned pole pieces constitutes a sodium ion-lithium ion combined pole piece unit C, and the combined battery cell 7 includes a sodium ion-
  • a lithium battery-lithium oxide-containing positive pole piece 3-4 and a sodium battery-polyanion positive pole piece 3-5 are respectively arranged, wherein the lithium battery-lithium oxide-containing positive pole piece 3-4 is arranged at one end of the lithium ion battery negative pole piece 3-1 disposed adjacent to the sodium ion-lithium ion combined pole piece unit C, and the sodium battery-polyanion positive pole piece 3-5 is arranged adjacent to the sodium ion-lithium ion combined pole piece unit C.
  • One end of the pole piece 3-3 is set.
  • the combined battery cell 8 is composed of a lithium-ion electrode unit B, which includes 50 lithium-ion battery-type lithium oxide-containing positive electrode sheets and 51 lithium-ion battery negative electrode sheets.
  • the lithium-ion electrode unit B the lithium-ion battery-type lithium oxide-containing positive electrode sheets and the lithium-ion battery negative electrode sheets are repeatedly arranged in sequence, and a separator is arranged between the lithium-ion battery-type lithium oxide-containing positive electrode sheets and the lithium-ion battery negative electrode sheets.
  • the combined battery cell 9 is composed of a sodium ion electrode unit A, which includes 50 sodium-ion type-polyanion type positive electrode sheets and 51 sodium ion battery negative electrode sheets.
  • a sodium ion electrode unit A which includes 50 sodium-ion type-polyanion type positive electrode sheets and 51 sodium ion battery negative electrode sheets.
  • the sodium-ion type-polyanion type positive electrode sheets and the sodium ion battery negative electrode sheets are repeatedly arranged in sequence, and a diaphragm is arranged between the sodium-ion type-polyanion type positive electrode sheets and the sodium ion battery negative electrode sheets.
  • Example 3 the battery prepared in Example 3 was used as a test object to conduct relevant performance tests.
  • the test battery was charged to 4.25V at 0.33C constant current and constant voltage, cut off at 0.02C, and then discharged to 2.8V at 0.33C.
  • the capacity, average voltage and cell mass were recorded.
  • the tested batteries were placed in a 45°C constant temperature box, charged at 1C constant current and constant voltage, cut off at 0.02C, and then discharged at 1C to 80% SOH, and the number of cycles was recorded.
  • the lithium battery-phosphate type positive electrode sheet, lithium battery-lithium oxide type positive electrode sheet, sodium battery-polyanion type positive electrode sheet and composite negative electrode sheet, lithium ion battery negative electrode sheet, and sodium ion battery negative electrode sheet prepared in Example 1 are used in different combinations to prepare different combined battery cells, and then the battery is prepared according to the following method: the positive electrode sheet and the negative electrode sheet are arranged in sequence, and each electrode sheet is separated by a diaphragm, and the combined battery cell is prepared by a lamination or winding process; then the combined battery cell is placed in a battery shell, and then the battery shell is subjected to treatments such as welding the pole ears and baking, and after the moisture content is tested to be qualified, an appropriate amount of electrolyte is injected into the battery shell, and the battery is packaged, and the battery is prepared by aging, forming, and exhausting the package.
  • the separator used is a polyethylene film.
  • the combined battery cell 10 includes 15 lithium battery-type lithium oxide-containing positive electrode sheets, 10 lithium battery-type phosphate-type positive electrode sheets, 25 sodium battery-type polyanion-type positive electrode sheets, 49 composite negative electrode sheets, 1 lithium battery negative electrode sheet, and 1 sodium battery negative electrode sheet.
  • the lithium battery-type lithium oxide-containing positive electrode sheet, the composite negative electrode sheet, the sodium battery-type polyanion-type positive electrode sheet, the composite negative electrode sheet, and the lithium battery-type lithium oxide-containing positive electrode sheet are repeatedly arranged in sequence, and the separator arranged between the above-mentioned electrodes constitutes a sodium ion-lithium ion combined electrode sheet unit D.
  • the sodium battery negative electrode active coating of the composite negative electrode sheet is arranged with the sodium battery positive electrode sheet
  • the lithium battery positive electrode sheet is arranged with the lithium battery negative electrode active coating of the composite negative electrode sheet
  • the separator is arranged between the above-mentioned positive electrode sheet and the negative electrode sheet.
  • one lithium ion battery negative electrode sheet and one sodium ion battery negative electrode sheet are respectively arranged at both ends of the sodium ion-lithium ion combination electrode sheet unit D, wherein the lithium ion battery negative electrode sheet is arranged adjacent to one end of the lithium ion battery positive electrode sheet arranged in the sodium ion-lithium ion combination electrode sheet unit D, and the sodium ion battery negative electrode sheet 1 is arranged adjacent to one end of the sodium ion battery positive electrode sheet arranged in the sodium ion-lithium ion combination electrode sheet unit D.
  • the combined battery cell 11 includes 15 lithium battery-type lithium oxide-containing positive electrode sheets, 10 lithium battery-phosphate-type positive electrode sheets, 25 sodium battery-type polyanion-type positive electrode sheets, 1 composite negative electrode sheet, 25 lithium ion battery negative electrode sheets, and 25 sodium ion battery negative electrode sheets.
  • the sodium battery-polyanion-type positive electrode sheet and the sodium ion battery negative electrode sheet are sequentially arranged, and the separators arranged between the above-mentioned electrode sheets constitute the sodium ion electrode sheet unit A; the lithium battery-type lithium oxide-containing positive electrode sheet and the lithium ion battery negative electrode sheet are sequentially arranged to form the sodium ion electrode sheet unit A.
  • the combined battery cell 11 includes the above-mentioned sodium ion pole piece unit A, the above-mentioned lithium ion pole piece unit B and a sodium ion-lithium ion pole piece unit D, the above-mentioned sodium ion pole piece unit A and the lithium ion pole piece unit B are connected by a composite negative pole piece, at the connection, the composite negative pole piece is arranged between the sodium ion battery positive pole piece of the sodium ion pole piece unit A and the lithium ion battery positive pole piece of the lithium ion pole piece unit B, on both sides of the composite negative pole piece, the sodium ion battery positive pole piece is arranged towards the sodium ion battery negative electrode active coating of the composite negative pole piece, and the lithium ion battery positive pole piece is arranged towards the lithium ion battery negative electrode active coating of the composite negative pole piece, and the sodium ion battery positive pole piece is arranged towards the lithium ion battery negative electrode active coating of the composite negative pole piece, and the sodium ion battery positive pole
  • the above-mentioned lithium ion battery positive pole piece, the composite negative pole piece, and the sodium ion battery positive pole piece are arranged in sequence, and the diaphragm arranged between the above-mentioned pole pieces constitute the sodium ion-lithium ion combined pole piece unit D.
  • the combined battery cell 12 is composed of a lithium-ion electrode unit B, which includes 25 lithium-ion battery-lithium oxide-containing positive electrode sheets, 25 lithium-ion battery-phosphate-type positive electrode sheets and 51 lithium-ion battery negative electrode sheets.
  • a lithium-ion electrode unit B which includes 25 lithium-ion battery-lithium oxide-containing positive electrode sheets, 25 lithium-ion battery-phosphate-type positive electrode sheets and 51 lithium-ion battery negative electrode sheets.
  • the lithium-ion battery-lithium oxide-containing positive electrode sheets, the lithium-ion battery negative electrode sheets, and the lithium-ion battery-phosphate-type positive electrode sheets are repeatedly arranged in sequence, and a separator is arranged between the positive electrode sheets and the negative electrode sheets.
  • the combined battery cell 13 is composed of a sodium ion electrode unit A, which includes 50 sodium-ion battery-polyanion positive electrode sheets and 51 sodium ion battery negative electrode sheets.
  • a sodium ion electrode unit A which includes 50 sodium-ion battery-polyanion positive electrode sheets and 51 sodium ion battery negative electrode sheets.
  • the sodium-ion battery-polyanion positive electrode sheets and the sodium ion battery negative electrode sheets are repeatedly arranged in sequence, and a diaphragm is arranged between the sodium-ion battery-polyanion positive electrode sheets and the sodium ion battery negative electrode sheets.
  • the sodium-ion battery-polyanion positive electrode plate and the sodium-ion battery negative electrode plate are repeatedly arranged in sequence.
  • Example 4 the battery prepared in Example 4 was used as a test object to conduct relevant performance tests.
  • the test battery was charged to 4.25V at 0.33C constant current and constant voltage, cut off at 0.02C, and then discharged to 2.8V at 0.33C.
  • the capacity, average voltage and cell mass were recorded.
  • the tested batteries were placed in a 45°C constant temperature box, charged at 1C constant current and constant voltage, cut off at 0.02C, and then discharged at 1C to 80% SOH, and the number of cycles was recorded.
  • the combined battery 10 and the combined battery 11 respectively integrate the positive electrode sheet of the lithium-ion battery and the positive electrode sheet of the sodium-ion battery in the same combined battery in different forms, thereby significantly improving the energy density of the combined battery, significantly reducing the DC impedance, and significantly improving the cycle performance.

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Abstract

一种组合电芯，组合电芯包括正极极片、负极极片和隔膜，正极极片包括钠离子电池正极极片、锂离子电池正极极片、复合正极极片中的至少两种，负极极片包括钠离子电池负极极片、锂离子电池负极极片、复合负极极片中的至少两种。

Description

组合电芯及应用其的电池
本申请要求在2023年05月23日提交中国专利局、申请号为2023106064449的中国专利申请的优先权，以上申请的全部内容通过引用结合在本申请中。
技术领域
本申请属于电池技术领域，具体地，涉及一种组合电芯及应用其的电池。
背景技术
锂离子电池能量密度高，但原料成本持续增长。钠离子电池的电化学性能稳定、成本及安全性优势显著，但能量密度低、循环寿命短。如何高效发挥钠离子电池、锂离子电池互补优势一直是行业难点。行业中一般采用电池PACK方式进行具有不同电芯的电池组合，但电池间寿命老化规律差异、SOC-OCV差异等问题需要BMS技术精细控制和管理，且常用的CMP(Cell-Module-Pack)三级构架空间利用率低、能量密度低。
技术问题
本申请通过提供一种组合电芯以及应用其的电池，以使同一电芯能够兼具锂离子电池、钠离子电池的性能优势，进一步提高电池的能量密度和循环性能。
技术解决方案
根据本申请的一个方面，提供一种组合电芯：组合电芯包括正极极片、负极极片和隔膜，正极极片包括钠离子电池正极极片、锂离子电池正极极片、复合正极极片中的至少两种，负极极片包括钠离子电池负极极片、锂离子电池负极极片、复合负极极片中的至少两种；钠离子电池正极极片的正极活性涂层含有适用于钠离子电池的第一正极活性材料；锂离子电池正极极片中的正极活性涂层含有适用于锂离子电池的第二正极活性材料；复合正极极片包括分别设置在集流体的两个背对侧面上的钠离子电池正极活性涂层和锂离子电池正极活性涂层，钠离子电池正极活性涂层中含有适用于钠离子电池的第三正极活性材料，锂离子电池正极活性涂层中含有适用于锂离子电池的第四正极活性材料；钠离子电池负极极片 中的负极涂层含有适用于钠离子电池的第一负极活性材料；锂离子电池负极极片中的负极涂层含有适用于锂离子电池的第二负极活性材料；复合负极极片包括分别设置在集流体的两个背对侧面上的钠离子电池负极活性涂层和锂离子电池负极活性涂层，钠离子电池负极活性涂层中含有适用于钠离子电池的第一负极活性材料，锂离子电池负极活性涂层中含有适用于锂离子电池的第二负极活性材料。
根据本申请的另一个方面，提供一种电池，该电池包括如上所述组合电芯，该电池为锂离子电池或钠离子电池或钾离子电池。本申请提供的电池兼具良好的能量密度以及循环性能。
技术效果
由于锂离子电池型正极活性材料和钠离子电池型正极活性材料特性差异明显，若为了使上述两种材料集成在同一电芯中而将上述两种材料组合制浆涂布，往往难以避免浆料分散不均、涂布效果不佳的问题，进而难以制得具有良好电性能的正极极片。而在本申请所提供的组合电芯中，将锂离子电池型正极活性材料和钠离子电池型正极活性材料分别制成锂离子电池正极极片和钠离子电池正极极片，或者通过将锂离子电池型正极活性材料、钠离子电池型正极活性材料所分别形成的正极活性涂层分设于集流体的两侧制成复合正极极片，直接避免了上述问题。本申请提供的组合电芯能够充分发挥锂离子电池、钠离子电池的协同性能优势，兼具能量密度高、循环性能佳的特点。
附图说明
图1为实施例2所制得的组合电芯1的结构示意图；
图2为实施例2所制得的组合电芯2的结构示意图；
图3为实施例3所制得的组合电芯7的结构示意图。
本发明的实施方式
在一实施例中，组合电芯包括以下极片单元中的至少两种：钠离子极片单元A、锂离子极片单元B、钠离子-锂离子组合极片单元C、钠离子-锂离子组合极片单元D；钠离子极片单元A包括钠离子电池正极极片、隔膜、钠离子电池负极极片；锂离子极片单元B包括锂离子电池正极极片、隔膜、锂离子电池负极极片；钠离子-锂离子组合极片单元C包括复合正极极片、隔膜、钠离子电池负极极片、锂离 子电池负极极片；钠离子-锂离子组合极片单元D包含钠离子电池正极极片、锂离子电池正极极片、隔膜、复合负极极片。
在一实施例中，通过设置构建钠离子极片单元A、锂离子极片单元B、钠离子-锂离子组合极片单元C、钠离子-锂离子组合极片单元D，使得含有适用于钠离子电池的正极活性材料、适用于锂离子电池的正极活性材料的不同正极极片都能够与合适的负极极片相互搭配，使得导电粒子能够在不同种类的正极极片之间顺畅传输。
在一实施例中，组合电芯至少包括钠离子极片单元A、锂离子极片单元B和衔接极片单元，钠离子极片单元A和锂离子极片单元B之间通过衔接极片单元衔接，衔接极片单元选在钠离子-锂离子组合极片单元C、钠离子-锂离子组合极片单元D中的至少一个。
在一实施例中，第一正极活性材料、第三正极活性材料独立地包括适用于钠离子电池的过渡金属氧化物类正极材料、聚阴离子型正极材料、普鲁士蓝类化合物正极材料、普鲁士白类化合物正极材料中的至少一种；第二正极活性材料、第四正极活性材料独立地包括适用于锂离子电池的磷酸盐类正极材料、含锂氧化物材料中的至少一种；第一负极活性材料包括适用于钠离子电池的硬碳、软碳、合金型负极活性材料、钛基负极活性材料中的至少一种；第二负极活性材料包括适用于锂离子电池的人造石墨、天然石墨、硅负极、硬碳、软碳中的至少一种。
在一实施例中，第一正极活性材料、第三正极活性材料独立地包括过渡金属氧化物类正极材料，第二正极活性材料、第四正极活性材料独立地包括磷酸盐类正极材料。由此得到的组合电芯具有良好的稳定性，在应用的过程中，通过使磷酸盐类正极材料(锂离子电池型正极活性材料)和过渡金属氧化物正极材料(钠离子电池型正极活性材料)同时充放电，能够使组合电芯表现出优秀的循环性能。
在一实施例中，第一正极活性材料、第三正极活性材料独立地包括聚阴离子型正极材料，第二正极活性材料、第四正极活性材料独立地包括过含锂氧化物材料类正极材料。在本申请所提供的组合电芯中，集成了上述两种正极活性材料的组合电芯具有较高的能量密度和良好的循环稳定性。
在一实施例中，钠离子电池正极极片包括聚阴离子型正极极片，该聚阴离子型正极极片所含有的第一正极活性材料为聚阴离子型正极材料(钠离子电池型正极活性材料)，锂离子电池正极极片包括磷酸 盐型正极极片和含锂氧化物型正极极片，上述磷酸盐型正极极片所含有的第二正极活性材料为磷酸盐类正极材料(锂离子电池型正极活性材料)，上述含锂氧化物型正极极片所含有的第二正极活性材料为含锂氧化物正极材料(锂离子电池型正极活性材料)。在本申请所提供的组合电芯中，集成了上述三种正极活性材料的组合电芯同时兼具能量密度高、循环稳定性高、安全性高的优良特性。
在一实施例中，在钠离子电池正极极片中，其所包括的正极活性涂层的平均面密度为S1n，第一正极活性材料在含有其的钠离子电池正极极片中的质量含量为W1n，钠离子电池正极极片的单位面积累积容量其中，i表示钠离子电池正极极片的数量；在锂离子电池正极极片中，其所包括的正极活性涂层的平均面密度为S2n，第二正极活性材料在含有其的锂离子电池正极极片中的质量含量为W2n，锂离子电池正极极片的单位面积累积容量其中，k表示锂离子电池正极极片的数量；在复合正极极片中，钠离子电池正极活性涂层的平均面密度为S3n，第三正极活性材料在含有其的钠离子电池正极活性涂层中的质量含量为W3n，锂离子电池正极活性涂层的平均面密度为S4n，第四正极活性材料在含有其的锂离子电池正极活性涂层汇总的质量含量为W4n，复合正极极片的数量为h，钠离子电池正极活性涂层的单位面积累积容量锂离子电池正极活性涂层的单位面积累积容量组合电芯满足，(C2+C4)/(C1+C3)＝0.5～2.5。
通过使组合电芯满足(C2+C4)/(C1+C3)＝0.5～2.5，强化适用于钠离子电池的正极活性材料和适用于锂离子电池的正极活性材料之间的协同效果，使得组合电芯的能量密度、循环性能得到进一步提高。
在一实施例中，钠离子电池正极极片和锂离子电池正极极片的搭配满足，i/k＝0.005～200。
在一实施例中，钠离子电池正极极片和锂离子电池正极极片的搭配满足，i/k＝0.01～100。
在一实施例中，i≤200，k≤200。
在一实施例中，钠离子电池正极极片的厚度为100～300μm，锂离子电池正极极片的厚度为100～400μm，负极极片的厚度为100～500μm。
在一实施例中，钠离子电池正极极片的正极活性涂层平均面密度S1n＝30～500g/m2，锂离子电池正极极片的正极活性涂层平均面密度S2n＝50～450g/m2。
实施例1
在本实施例下述内容中，为了清楚区分：将下述钠离子电池正极极片所采用的正极活性材料记为“第一正极活性材料”，将下述锂离子电池正极极片所采用的正极活性材料记为“第二正极活性材料”；将下述复合正极极片中的钠离子电池正极活性涂层中所采用的正极活性材料记为“第三正极活性材料”，将下述复合正极极片中的锂离子电池正极活性涂层中所采用的正极材料记为“第四正极活性材料”；将下述钠离子电池负极极片所采用的负极活性材料记为“第一负极活性材料”；将下述锂离子电池负极极片所采用的负极活性材料记为“第二负极活性材料”；将下述复合正极极片中的钠离子电池负极活性涂层中所采用的负极活性材料记为“第三负极活性材料”，将下述复合负极极片中的锂离子电池负极活性涂层中所采用的负极活性材料记为“第四负极活性材料”；。
1.正极极片的制备
(1)钠离子电池正极极片的制备
1)钠电型-过渡金属氧化物正极极片
采用层状过渡金属氧化物NaMnO2作为第一正极活性材料，以NaMnO2、粘结剂PVDF、导电剂乙炔黑按照80：10：10的质量比组合均匀制成正极涂布浆料，然后在正极集流体的两个背对设置的侧面上分别涂布上述正极涂布浆料，干燥，从而在正极集流体的两个侧面形成对称设置的正极活性涂层，制得钠电型-过渡金属氧化物正极极片，其所包括的正极活性涂层的单面平均面密度为30～500g/m2。
2)钠电型-聚阴离子型正极极片
采用聚阴离子化合物NASICON作为第一正极活性材料，以NASICON、粘结剂PVDF、导电剂乙炔黑按照90：5：5的质量比组合均匀制成正极涂布浆料，然后在正极集流体的两个背对设置的侧面上分别涂布上述正极涂布浆料，干燥，从而在正极集流体的两个侧面形成对称设置的正极活性涂层，制得钠电型-聚阴离子型正极极片，其所包括的正极活性涂层的单面平均面密度为50～500g/m2。
(2)锂离子电池正极极片的制备
1)锂电型-磷酸盐型正极极片
采用磷酸盐LiFePO4作为第二正极活性材料，以LiFePO4、粘结剂PVDF、导电剂乙炔黑按照97:2:1进行组合的质量比组合均匀制成正极涂布浆料，然后在正极集流体的两个背对设置的侧面上分别涂布上 述正极涂布浆料，干燥，从而在正极集流体的两个侧面形成对称设置的正极活性涂层，制得锂电型-磷酸盐型正极极片，其所包括的正极活性涂层的单面平均面密度为80-450g/m2。
2)锂电型-含锂氧化物型正极极片
采用NCM622作为第二正极活性材料，以NCM622、粘结剂PVDF、导电剂乙炔黑按照97:2:1进行组合的质量比组合均匀制成正极涂布浆料，然后在正极集流体的两个背对设置的侧面上分别涂布上述正极涂布浆料，干燥，从而在正极集流体的两个侧面形成对称设置的正极活性涂层，制得锂电型-含锂氧化物型正极极片，其所包括的正极活性涂层的单面平均面密度为50-450g/m2。
(3)复合正极极片的制备
采用聚阴离子化合物NASICON作为第三正极活性材料、采用NCM622作为第四正极活性材料。将NASICON、粘结剂PVDF、导电剂乙炔黑按照90：5：5的质量比组合制成第一正极涂布浆料，将NCM622、粘结剂PVDF、导电剂乙炔黑按照97:2:1的质量比组合制成第二正极涂布浆料；然后在正极集流体的其中一个侧面上涂布上述第一正极涂布浆料，干燥，从而在正极集流体的一个侧面形成钠离子电池正极活性涂层；接着，在正极集流体的另一个侧面上涂布上述第二正极涂布浆料，干燥，从而在正极集流体的另一个侧面形成锂离子电池正极活性涂层；通过上述步骤制得复合正极极片。
2.负极极片的制备
(1)钠离子电池负极极片的制备
采用硬碳作为第一负极活性材料，将硬碳、导电剂乙炔黑、粘结剂羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)按94：1：2：3的质量比组合制成负极涂布浆料，然后在负极集流体的两个背对设置的侧面上分别涂布上述负极涂布浆料，干燥，从而在负极集流体的两个侧面形成对称设置的负极活性涂层，制得钠离子电池负极极片。
(2)锂离子电池负极极片的制备
采用天然石墨作为第二负极活性材料，将天然石墨、导电剂乙炔黑、粘结剂羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)按94：1：2：3的质量比组合制成负极涂布浆料，然后在负极集流体的两个背对设置的侧面上分别涂布上述负极涂布浆料，干燥，从而在负极集流体的两个侧面形成对称设置的负极活性涂层， 制得锂离子电池负极极片。
(3)复合负极极片的制备
采用硬碳作为第三负极活性材料、采用天然石墨作为第四负极活性材料。将硬碳、导电剂乙炔黑、粘结剂羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)按94：1：2：3的质量比组合制成第一负极涂布浆料，将天然石墨、导电剂乙炔黑、粘结剂羧甲基纤维素钠(CMC)、丁苯橡胶(SBR)按94：1：2：3的质量比组合制成第二负极涂布浆料；然后在负极集流体的其中一个侧面上涂布上述第一负极涂布浆料，干燥，从而在负极集流体的一个侧面形成钠离子电池负极活性涂层；接着，在负极集流体的另一个侧面上涂布上述第二负极涂布浆料，干燥，从而在负极集流体的另一个侧面形成锂离子电池负极活性涂层；通过上述步骤制得复合负极极片。
实施例2
本实施例采用实施例1所制得的锂电型-磷酸盐型正极极片、钠电型-过渡金属氧化物正极极片与复合负极极片、锂离子电池负极极片、钠离子电池负极极片按照不同的组合方式制备不同的组合电芯，然后按照以下方法制备电池：将正极极片、负极极片依次间隔设置，各极片之间均采用隔膜进行分隔，通过叠片或者卷绕的工艺制得组合电芯；然后将组合电芯置于电池壳体中，接着对电池壳体进行焊接极耳、烘烤等处理，待水分含量检测合格后向电池壳体中注入适量电解液，封装，通过老化，化成，抽气封装，制得电池。
在本实施例中，所采用的隔膜为聚乙烯膜。
对本实施例采用不同正极极片和负极极片搭配的组合电芯进行编号，具体情况在表1中展示。
表1.实施例2中各组合电芯的正极极片、负极极片搭配情况

组合电芯1包括25片锂电型-磷酸盐型正极极片1-1、49片复合负极极片1-2、25片钠电型-过渡金属氧化物正极极片1-3、1片锂离子电池负极极片1-4、1片钠离子电池负极极片1-5。如图1所示，在上述极片中：复合负极极片1-2设置在锂电型-磷酸盐型正极极片1-1和钠电型-过渡金属氧化物正极极片1-3之间，在复合负极极片1-2两侧，朝向复合负极极片1-2的钠电池负极活性涂层1-22设置钠电型-过渡金属氧化物正极极片1-3，朝向复合负极极片1-2的锂电池负极活性涂层1-21设置锂电型-磷酸盐型正极极片1-1；在上述极片中，以锂电型-磷酸盐型正极极片1-1、复合负极极片1-2、钠电型-过渡金属氧化物正极极片1-3、复合负极极片1-2、锂电型-磷酸盐型正极极片1-1依次重复设置以及设置在上述极片之间的隔膜构成钠离子-锂离子组合极片单元D，如图1所示，组合电芯1包括一个钠离子-锂离子组合极片单元D，此外，在该钠离子-锂离子组合极片单元D的两端分别设置1片锂离子电池负极极片1-4、1片钠离子电池负极极片1-5，其中，锂离子电池负极极片1-4相邻钠离子-锂离子组合极片单元D中设置锂电型-磷酸盐型正极极片1-1的一端设置，钠离子电池负极极片1-5相邻钠离子-锂离子组合极片单元D中设置钠电型-过渡金属氧化物正极极片1-3的一端设置。
组合电芯2包括25片锂电型-磷酸盐型正极极片2-1、1片复合负极极片2-2、25片钠电型-过渡金属氧化物正极极片2-3、25片钠离子电池负极极片2-5、25片锂离子电池负极极片2-4。如图2所示，在上述极片中：以25片钠电型-过渡金属氧化物正极极片2-3、25片钠离子电池负极极片2-5依次设置以及设置在上述极片之间的隔膜2-6构成钠离子极片单元A，25片锂电型-磷酸盐型正极极片2-1、25片锂离子电池负极极片2-4依次设置以及设置在上述极片之间的隔膜2-6构成锂离子极片单元B。组合电芯2包括一个上述钠离子极片单元A、一个上述锂离子极片单元B和一个钠离子-锂离子极片单元D，上述 钠离子极片单元A和锂离子极片单元B通过一片复合负极极片2-2衔接，在衔接处，复合负极极片2-2设置在钠离子极片单元A的钠电型-过渡金属氧化物正极极片2-3和锂离子极片单元B的锂电型-磷酸盐型正极极片2-1之间，在复合负极极片2-2两侧，朝向复合负极极片2-2的钠离子电池负极活性涂层2-22设置钠电型-过渡金属氧化物正极极片2-3，朝向复合负极极片2-2的锂离子电池负极活性涂层2-21设置锂电型-磷酸盐型正极极片2-1，以上述衔接处的1片锂电型-磷酸盐型正极极片2-1、1片复合负极极2-2、1片钠电型-过渡金属氧化物正极极片2-3依次设置以及设置在上述极片之间的隔膜构成钠离子-锂离子组合极片单元D。
组合电芯3由一个锂离子极片单元B构成，上述锂离子极片单元B包括50片锂电型-磷酸盐型正极极片和51片锂离子电池负极极片，在锂离子极片单元B中，锂电型-磷酸盐型正极极片、锂离子电池负极极片依次重复设置，且在锂电型-磷酸盐型正极极片、锂离子电池负极极片之间设置隔膜。
组合电芯4由一个钠离子极片单元A构成，上述钠离子极片单元A包括50片钠电型-过渡金属氧化物正极极片和51片钠离子电池负极极片，在钠离子极片单元A中，钠电型-过渡金属氧化物正极极片、钠离子电池负极极片依次重复设置，且在钠电型-过渡金属氧化物正极极片、钠离子电池负极极片之间设置隔膜。
测试例1
1.参试对象
本测试例以实施例2所制得的电池作为参试对象，进行相关性能测试。
2.测试内容
(1)能量密度
将参试的电池以0.33C恒流恒压充电至4.25V，0.02C截止，然后0.33C放电至2.8V，记录容量，平均电压和电芯质量，按照以下公式计算电池的能量密度：能量密度＝容量*平均电压/电池质量。
(2)直流阻抗
将参试的电池以0.33C恒流恒压充电至4.25V，0.02C截止，然后0.33C放电90min，搁置10min，记录搁置末端电压V1；然后以2C(电流I)放电10s，记录放电末端电压V2，按照以下公式计算电池的直 流阻抗：直流阻抗＝|V1-V2|/I。
(3)循环性能
将参试的电池放在45℃恒温箱中，以1C恒流恒压充电，0.02C截止，然后以1C放电，循环至80％SOH，记录循环圈数。
3.测试结果
从本测试例的测试结果可以看出，分别以正极极片仅采用锂离子电池正极极片的组合电芯3、正极极片仅采用钠离子电池正极极片的组合电芯4作为参照，组合电芯1、组合电芯2分别以不同的形式将锂离子电池正极极片和钠离子电池正极极片集成在同一组合电芯中，由此使得组合电芯的能量密度得到明显的提高、直流阻抗得到明显的下降、循环性能得到明显的提升。
表2.测试例1的电池性能测试结果
实施例3
本实施例采用实施例1所制得的锂电型-含锂氧化物型正极极片、钠电型-聚阴离子型正极极片与复合负极极片、锂离子电池负极极片、钠离子电池负极极片按照不同的组合方式制备不同的组合电芯，然后按照以下方法制备电池：将正极极片、负极极依次间隔设置，各极片之间均采用隔膜进行分隔，通过叠片或者卷绕的工艺制得组合电芯；然后将组合电芯置于电池壳体中，接着对电池壳体进行焊接极耳、烘烤等处理，待水分含量检测合格后向电池壳体中注入适量电解液，封装，通过老化，化成，抽气封装，制得电池。
在本实施例中，所采用的隔膜为聚乙烯膜。
对本实施例采用不同正极极片和负极极片搭配的组合电芯进行编号，具体情况在表3中展示。
表3.实施例3中各组合电芯的正极极片、负极极片搭配情况
组合电芯5包括25片锂电型-含锂氧化物型正极极片、49片复合负极极片、25片钠电型-聚阴离子型正极极片、1片锂离子电池负极极片、1片钠离子电池负极极片。在上述极片中：复合负极极片设置在锂电型-含锂氧化物型正极极片和钠电型-聚阴离子型正极极片之间，在复合负极极片两侧，朝向复合负极极片的钠电池负极活性涂层设置钠电型-聚阴离子型正极极片，朝向复合负极极片的锂电池负极活性涂层设置锂电型-含锂氧化物型正极极片；在上述极片中，以锂电型-含锂氧化物型正极极片、复合负极极片、钠电型-聚阴离子型正极极片、复合负极极片、锂电型-含锂氧化物型正极极片依次重复设置以及设置在上述极片之间的隔膜构成钠离子-锂离子组合极片单元D，组合电芯5包括一个钠离子-锂离子组合极片单元D，此外，在此外，在该钠离子-锂离子组合极片单元D的两端分别设置1片锂离子电池负极极片、1片钠离子电池负极极片，其中，锂离子电池负极极片相邻钠离子-锂离子组合极片单元D 中设置锂电型-含锂氧化物型正极极片的一端设置，钠离子电池负极极片相邻钠离子-锂离子组合极片单元D中设置钠电型-聚阴离子型正极极片的一端设置。
组合电芯6包括25片锂电型-含锂氧化物型正极极片、1片复合负极极片、25片钠电型-聚阴离子型正极极片、25片钠离子电池负极极片、25片锂离子电池负极极片。在上述极片中：以25片钠电型-聚阴离子型正极极片、25片钠离子电池负极极片依次设置以及设置在上述极片之间的隔膜构成钠离子极片单元A，25片锂电型-含锂氧化物型正极极片、25片锂离子电池负极极片依次设置以及设置在上述极片之间的隔膜构成锂离子极片单元B。组合电芯1包括一个钠离子极片单元A、一个锂离子极片单元B和一个锂离子极片单元D，上述钠离子极片单元A和锂离子极片单元B通过一片复合负极极片衔接，在衔接处，复合负极极片设置在钠离子极片单元A的钠电型-聚阴离子型正极极片和锂离子极片单元B的锂电型-含锂氧化物型正极极片之间，在复合负极极片两侧，朝向复合负极极片的钠离子电池负极活性涂层设置钠电型-聚阴离子型正极极片，朝向复合负极极片的锂离子电池负极活性涂层设置锂电型-含锂氧化物型正极极片，以上述衔接处的1片锂电型-含锂氧化物型正极极片、1片复合负极极、1片钠电型-聚阴离子型正极极片依次设置以及设置在上述极片之间的隔膜构成钠离子-锂离子组合极片单元D。
组合电芯7包括49片复合正极极片3-2、1片锂电型-含锂氧化物型正极极片3-4、1片钠电型-聚阴离子型正极极片3-5、25片锂离子电池负极极片3-1、25片钠离子电池负极极片3-3。如图3所示，在上述极片中：复合正极极片3-2设置在锂离子电池负极极片3-1和钠离子电池负极极片3-3之间，在复合正极极片3-2两侧，朝向复合正极极片3-2的钠电池正极活性涂层3-22设置钠离子电池负极极片3-3，朝向复合正极极片3-2的锂电池正极活性涂层3-21设置钠离子电池负极极片3-3；在上述极片中，以锂离子电池负极极片3-1、复合正极极片3-2、钠离子电池负极极片3-3、复合正极极片3-2、锂离子电池负极极片3-1依次重复设置以及设置在上述极片之间的隔膜3-6构成钠离子-锂离子组合极片单元C，组合电芯7包括一个钠离子-锂离子组合极片单元C，此外，在此外，在该钠离子-锂离子组合极片单元C的两端分别设置1片锂电型-含锂氧化物型正极极片3-4、1片钠电型-聚阴离子型正极极片3-5，其中，锂电型-含锂氧化物型正极极片3-4相邻钠离子-锂离子组合极片单元C中设置锂离子电池负极极片3-1的一端设置，钠电型-聚阴离子型正极极片3-5相邻钠离子-锂离子组合极片单元C中设置钠离子电池负 极极片3-3的一端设置。
组合电芯8由一个锂离子极片单元B构成，上述锂离子极片单元B包括50片锂电型-含锂氧化物型正极极片和51片锂离子电池负极极片，在锂离子极片单元B中，锂电型-含锂氧化物型正极极片、锂离子电池负极极片依次重复设置，且在锂电型-含锂氧化物型正极极片、锂离子电池负极极片之间设置隔膜。
组合电芯9由一个钠离子极片单元A构成，上述钠离子极片单元A包括50片钠电型-聚阴离子型正极极片和51片钠离子电池负极极片，在钠离子极片单元A中，钠电型-聚阴离子型正极极片、钠离子电池负极极片依次重复设置，且在钠电型-聚阴离子型正极极片、钠离子电池负极极片之间设置隔膜。
测试例2
1.参试对象
本测试例以实施例3所制得的电池作为参试对象，进行相关性能测试。
2.测试内容
(1)能量密度
将参试的电池以0.33C恒流恒压充电至4.25V，0.02C截止，然后0.33C放电至2.8V，记录容量，平均电压和电芯质量，按照以下公式计算电池的能量密度：能量密度＝容量*平均电压/电池质量。
(2)直流阻抗
将参试的电池以0.33C恒流恒压充电至4.25V，0.02C截止，然后0.33C放电90min，搁置10min，记录搁置末端电压V1；然后以2C(电流I)放电10s，记录放电末端电压V2，按照以下公式计算电池的直流阻抗：直流阻抗＝|V1-V2|/I。
(3)循环性能
将参试的电池放在45℃恒温箱中，以1C恒流恒压充电，0.02C截止，然后以1C放电，循环至80％SOH，记录循环圈数。
3.测试结果
从本测试例的测试结果可以看出，分别以正极极片仅采用锂离子电池正极极片的组合电芯8、正 极极片仅采用钠离子电池正极极片的组合电芯9作为参照，组合电芯5、组合电芯6分别以不同的形式将锂离子电池正极极片和钠离子电池正极极片集成在同一组合电芯中，而组合电芯7则分别适用于锂离子电池正极的正极活性材料、适用于钠离子电池正极的正极活性材料集成在同一复合正极极片中，上述两种不同的集成方式都能够使得组合电芯的能量密度得到明显的提高、直流阻抗得到明显的下降、循环性能得到明显的提升。
表4.测试例2的电池性能测试结果
实施例4
本实施例采用实施例1所制得的锂电型-磷酸盐型正极极片、锂电型-含锂氧化物型正极极片、钠电型-聚阴离子型正极极片与复合负极极片、锂离子电池负极极片、钠离子电池负极极片按照不同的组合方式制备不同的组合电芯，然后按照以下方法制备电池：将正极极片、负极极依次间隔设置，各极片之间均采用隔膜进行分隔，通过叠片或者卷绕的工艺制得组合电芯；然后将组合电芯置于电池壳体中，接着对电池壳体进行焊接极耳、烘烤等处理，待水分含量检测合格后向电池壳体中注入适量电解液，封装，通过老化，化成，抽气封装，制得电池。
在本实施例中，所采用的隔膜为聚乙烯膜。
对本实施例采用不同正极极片和负极极片搭配的组合电芯进行编号，具体情况在表5中展示。
表5.实施例4中各组合电芯的正极极片、负极极片搭配情况

组合电芯10包括15片锂电型-含锂氧化物型正极极片、10片锂电型-磷酸盐型正极极片、25片钠电型-聚阴离子型正极极片、49片复合负极极片、1片锂电池负极极片、1片钠电池负极极片。在组合电芯10中：锂电型-含锂氧化物型正极极片、复合负极极片、钠电型-聚阴离子型正极极片、复合负极极片、锂电型-含锂氧化物型正极极片依次重复设置以及设置在上述极片之间的隔膜构成钠离子-锂离子组合极片单元D，在钠离子-锂离子组合极片单元D中，在复合负极极片两侧，朝向复合负极极片的钠电池负极活性涂层设置钠电池正极极片，朝向复合负极极片的锂电池负极活性涂层设置锂电池正极极片，上述正极极片和负极极片之间设有隔膜，。在组合芯片10中，于钠离子-锂离子组合极片单元D的两端分别设置1片锂离子电池负极极片、1片钠离子电池负极极片，其中，锂离子电池负极极片相邻钠离子-锂离子组合极片单元D中设置锂离子电池正极极片的一端设置，钠离子电池负极极片1-相邻钠离子-锂离子组合极片单元D中设置钠离子电池正极极片的一端设置。
组合电芯11包括15片锂电型-含锂氧化物型正极极片、10片锂电型-磷酸盐型正极极片、25片钠电型-聚阴离子型正极极片、1片复合负极极片、25片锂离子电池负极极片、25片钠离子电池负极极片。在组合电芯11中：以钠电型-聚阴离子型正极极片、钠离子电池负极极片依次设置以及设置在上述极片之间的隔膜构成钠离子极片单元A；以锂电型-含锂氧化物型正极极片、锂离子电池负极极片依次设置以 及设置在上述极片之间的隔膜构成锂离子极片单元B；组合电芯11包括一个上述钠离子极片单元A、一个上述锂离子极片单元B和一个钠离子-锂离子极片单元D，上述钠离子极片单元A和锂离子极片单元B通过一片复合负极极片衔接，在衔接处，复合负极极片设置在钠离子极片单元A的钠离子电池正极极片和锂离子极片单元B的锂离子电池正极极片之间，在复合负极极片两侧，朝向复合负极极片的钠离子电池负极活性涂层设置钠离子电池正极极片，朝向复合负极极片的锂离子电池负极活性涂层设置锂离子电池正极极片，以上述衔接处的1片锂离子电池正极极片、1片复合负极极、1片钠离子电池正极极片依次设置以及设置在上述极片之间的隔膜构成钠离子-锂离子组合极片单元D。
组合电芯12由一个锂离子极片单元B构成，上述锂离子极片单元B包括25片锂电型-含锂氧化物型正极极片、25片锂电型-磷酸盐型正极极片和51片锂离子电池负极极片，在锂离子极片单元B中，锂电型-含锂氧化物型正极极片、锂离子电池负极极片、锂电型-磷酸盐型正极极片依次重复设置，且在正极极片、负极极片之间设置隔膜。
组合电芯13由一个钠离子极片单元A构成，上述钠离子极片单元A包括50片钠电型-聚阴离子型正极极片和51片钠离子电池负极极片，在钠离子极片单元A中，钠电型-聚阴离子型正极极片、钠离子电池负极极片依次重复设置，且在钠电型-聚阴离子型正极极片、钠离子电池负极极片之间设置隔膜。
在组合电芯12中，所包括的钠电型-聚阴离子型正极极片、钠离子电池负极极片依次重复设置。
测试例3
1.参试对象
本测试例以实施例4所制得的电池作为参试对象，进行相关性能测试。
2.测试内容
(1)能量密度
将参试的电池以0.33C恒流恒压充电至4.25V，0.02C截止，然后0.33C放电至2.8V，记录容量，平均电压和电芯质量，按照以下公式计算电池的能量密度：能量密度＝容量*平均电压/电池质量。
(2)直流阻抗
将参试的电池以0.33C恒流恒压充电至4.25V，0.02C截止，然后0.33C放电90min，搁置10min， 记录搁置末端电压V1；然后以2C(电流I)放电10s，记录放电末端电压V2，按照以下公式计算电池的直流阻抗：直流阻抗＝|V1-V2|/I。
(3)循环性能
将参试的电池放在45℃恒温箱中，以1C恒流恒压充电，0.02C截止，然后以1C放电，循环至80％SOH，记录循环圈数。
3.测试结果
从本测试例的测试结果可以看出，分别以正极极片仅采用锂离子电池正极极片的组合电芯12、正极极片仅采用钠离子电池正极极片的组合电芯13作为参照，组合电芯10、组合电芯11分别以不同的形式将锂离子电池正极极片和钠离子电池正极极片集成在同一组合电芯中，由此使得组合电芯的能量密度得到明显的提高、直流阻抗得到明显的下降、循环性能得到明显的提升。
表6.测试例3的电池性能测试结果

Claims (10)

  1. 一种组合电芯，
    所述组合电芯包括正极极片、负极极片和隔膜，所述正极极片包括钠离子电池正极极片、锂离子电池正极极片、复合正极极片中的至少两种，所述负极极片包括钠离子电池负极极片、锂离子电池负极极片、复合负极极片中的至少两种；
    所述钠离子电池正极极片的正极活性涂层含有适用于钠离子电池的第一正极活性材料；所述锂离子电池正极极片中的正极活性涂层含有适用于锂离子电池的第二正极活性材料；所述复合正极极片包括分别设置在集流体的两个背对侧面上的钠离子电池正极活性涂层和锂离子电池正极活性涂层，所述钠离子电池正极活性涂层中含有适用于钠离子电池的第三正极活性材料，所述锂离子电池正极活性涂层中含有适用于锂离子电池的第四正极活性材料；
    所述钠离子电池负极极片中的负极涂层含有适用于钠离子电池的第一负极活性材料；所述锂离子电池负极极片中的负极涂层含有适用于锂离子电池的第二负极活性材料；所述复合负极极片包括分别设置在集流体的两个背对侧面上的钠离子电池负极活性涂层和锂离子电池负极活性涂层，所述钠离子电池负极活性涂层中含有适用于钠离子电池的第一负极活性材料，所述锂离子电池负极活性涂层中含有适用于锂离子电池的第二负极活性材料。
  2. 如权利要求1所述组合电芯，其中，所述组合电芯包括以下极片单元中的至少两种：钠离子极片单元A、锂离子极片单元B、钠离子-锂离子组合极片单元C、钠离子-锂离子组合极片单元D；
    所述钠离子极片单元A包括所述钠离子电池正极极片、所述隔膜、所述钠离子电池负极极片；所述锂离子极片单元B包括所述锂离子电池正极极片、所述隔膜、所述锂离子电池负极极片；所述钠离子-锂离子组合极片单元C包括所述复合正极极片、所述隔膜、所述钠离子电池负极极片、所述锂离子电池负极极片；所述钠离子-锂离子组合极片单元D包含所述钠离子电池正极极片、所述锂离子电池正极极片、所述隔膜、所述复合负极极片。
  3. 如权利要求2所述组合电芯，其中：
    所述组合电芯至少包括所述钠离子极片单元A、所述锂离子极片单元B和衔接极片单元，所述钠离 子极片单元A和所述锂离子极片单元B之间通过所述衔接极片单元衔接，所述衔接极片单元选在所述钠离子-锂离子组合极片单元C、所述钠离子-锂离子组合极片单元D中的至少一个。
  4. 如权利要求1所述组合电芯，其中：
    所述第一正极活性材料、所述第三正极活性材料独立地包括适用于钠离子电池的过渡金属氧化物类正极材料、聚阴离子型正极材料、普鲁士蓝类化合物正极材料、普鲁士白类化合物正极材料中的至少一种；
    所述第二正极活性材料、所述第四正极活性材料独立地包括适用于锂离子电池的磷酸盐类正极材料、含锂氧化物材料中的至少一种；
    所述第一负极活性材料包括适用于钠离子电池的硬碳、软碳、合金型负极活性材料、钛基负极活性材料中的至少一种；
    所述第二负极活性材料包括适用于锂离子电池的人造石墨、天然石墨、硅负极、硬碳、软碳中的至少一种。
  5. 如权利要求1～4任一项所述组合电芯，其中：
    在所述钠离子电池正极极片中，其所包括的正极活性涂层的平均面密度为S1n，所述第一正极活性材料在含有其的所述钠离子电池正极极片中的质量含量为W1n，所述钠离子电池正极极片的单位面积累积容量其中，i表示所述钠离子电池正极极片的数量；
    在所述锂离子电池正极极片中，其所包括的正极活性涂层的平均面密度为S2n，所述第二正极活性材料在含有其的所述锂离子电池正极极片中的质量含量为W2n，所述锂离子电池正极极片的单位面积累积容量其中，k表示所述锂离子电池正极极片的数量；
    在所述复合正极极片中，所述钠离子电池正极活性涂层的平均面密度为S3n，所述第三正极活性材料在含有其的所述钠离子电池正极活性涂层中的质量含量为W3n，所述锂离子电池正极活性涂层的平均面密度为S4n，所述第四正极活性材料在含有其的所述锂离子电池正极活性涂层汇总的质量含量为W4n，所述复合正极极片的数量为h，所述钠离子电池正极活性涂层的单位面积累积容量 所述锂离子电池正极活性涂层的单位面积累积容量
    所述组合电芯满足，(C2+C4)/(C1+C3)＝0.5～2.5。
  6. 如权利要求5所述组合电芯，其中：所述钠离子电池正极极片和所述锂离子电池正极极片的搭配满足，i/k＝0.005～200。
  7. 如权利要求6所述组合电芯，其中：i≤200，k≤200。
  8. 如权利要求7所述组合电芯，其中：所述钠离子电池正极极片的厚度为100～300μm，所述锂离子电池正极极片的厚度为100～400μm，所述负极极片的厚度为100～500μm。
  9. 如权利要求7所述组合电芯，其中：所述钠离子电池正极极片的正极活性涂层平均面密度S1n＝30～500g/m2，所述锂离子电池正极极片的正极活性涂层平均面密度S2n＝50～450g/m2。
  10. 一种电池，所述电池包括如权利要求1～9任一项所述组合电芯，所述电池为锂离子电池、钠离子电池、钾离子电池中的一种。
PCT/CN2023/112087 2023-05-23 2023-08-10 组合电芯及应用其的电池 Ceased WO2024239459A1 (zh)

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