WO2021184262A1 - Cellule de batterie au lithium-ion, son procédé de préparation et batterie au lithium-ion la comprenant - Google Patents

Cellule de batterie au lithium-ion, son procédé de préparation et batterie au lithium-ion la comprenant Download PDF

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Publication number
WO2021184262A1
WO2021184262A1 PCT/CN2020/080042 CN2020080042W WO2021184262A1 WO 2021184262 A1 WO2021184262 A1 WO 2021184262A1 CN 2020080042 W CN2020080042 W CN 2020080042W WO 2021184262 A1 WO2021184262 A1 WO 2021184262A1
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Prior art keywords
cell
lithium
silicon
battery
pole piece
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PCT/CN2020/080042
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English (en)
Chinese (zh)
Inventor
章婷
姜道义
陈志焕
崔航
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宁德新能源科技有限公司
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Priority to PCT/CN2020/080042 priority Critical patent/WO2021184262A1/fr
Priority to CN202080094446.9A priority patent/CN115039268A/zh
Publication of WO2021184262A1 publication Critical patent/WO2021184262A1/fr

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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
    • H01M10/04—Construction or manufacture in general
    • 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
    • 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

Definitions

  • This application relates to the technical field of lithium ion batteries, and in particular to a battery cell of a lithium ion battery, a preparation method thereof, and a lithium ion battery including the battery core.
  • the cell of a soft-packaged lithium-ion battery is wound from pole pieces, and there are usually varying degrees of volume expansion during the lithium insertion process, which causes the pole pieces to wrinkle and deform, and the wrinkle and deformation of the pole pieces will cause the charging process Lithium evolution occurs in the process, causing safety hazards.
  • the present application provides a cell of a lithium ion battery to reduce the probability of deformation of the pole piece, so as to at least improve the problem of lithium evolution in the cell caused by the deformation of the pole piece.
  • the first aspect of the present application provides a battery cell of a lithium ion battery, including a straight section and a bent section, and the battery cell is wound by a laminate including a positive pole piece, a negative pole piece and a separator;
  • the total number of winding turns of the battery core is N
  • the thickness of the laminated body in the straight section of the battery core is m 1 mm
  • a reserve is provided inside at least one designated turn of the bending section of the battery core.
  • a and g satisfy: 0.55m 1 N ⁇ 1000 g/a ⁇ 1.90m 1 N.
  • the number of the designated circles is 2 or 3, and the interval between two adjacent reserved spaces is 2-5 circle stacks.
  • the negative active material on the negative pole piece includes a silicon-based material.
  • the silicon-based material includes at least one of nano-silicon particles, SiO x , silicon-carbon composite material, or silicon alloy, where 0.5 ⁇ x ⁇ 1.6.
  • the average particle size of SiOx, silicon-carbon composite material or silicon alloy in the silicon-based material is 500 nm-30 ⁇ m; the average particle size of the nano silicon particles is less than 100 nm.
  • the silicon-based material further contains lithium and/or magnesium.
  • the second aspect of the application provides the method for preparing the battery cell provided in the first aspect of the application, including:
  • a third aspect of the present application provides a lithium ion battery including the battery cell provided in the first aspect of the application, the lithium ion battery further includes an electrolyte and a packaging film, the battery is immersed in the electrolyte and packaged In the packaging film.
  • the fourth aspect of the present application provides an electronic device, including the lithium ion battery provided in the third aspect of the present application.
  • wrinkle refers to the phenomenon of continuous bending of the separator and the pole piece
  • the wrinkle or deformation caused by the expansion of the battery cell can be improved, and at least the battery cell caused by the deformation can be improved Analyze the lithium problem.
  • Fig. 1 is a schematic diagram of a cell structure of a lithium-ion battery according to an embodiment of the present application
  • FIG. 2 is a top view of the battery cell of the lithium ion battery of Embodiment 4;
  • FIG. 3 is a thickness side view of the cell of the lithium ion battery of Embodiment 4; FIG.
  • the first aspect of the present application provides a lithium-ion battery cell, as shown in Figures 1-3, including a straight section 1 and a bent section 2.
  • the cell consists of a positive pole piece 6 and a negative pole piece 7. It is wound up with a laminated body of the separator,
  • the total number of winding turns of the battery core is N
  • the thickness of the laminated body in the straight section of the battery core is m 1 mm
  • a reserve is provided inside at least one designated turn of the bending section of the battery core.
  • Space 3 so that the distance g between the two points where the curvature of the innermost layer of the bending section 2 of the battery core and the outermost layer is greatest satisfies m 1 N ⁇ g ⁇ 1.87m 1 N; wherein the at least one designated circle In the range of N/4 to 3N/4; the unit volume capacity of the negative pole piece is a mAh/cm 3 , and 619 ⁇ a ⁇ 3000.
  • the straight section 1 of the battery cell refers to the two sections of the cell where the laminate body does not bend or bends less
  • the bending section 2 of the cell refers to the two ends of the cell where the laminate body is bent.
  • the laminate may specifically include a positive pole piece, a negative pole piece, and two-layer isolation films.
  • One of the two-layer isolation films is located between the positive pole piece and the negative pole piece, and the other layer is located On the other side of the positive pole piece, when the laminated body is wound to form a battery, the functions of the two isolation films are to separate the positive pole piece and the negative pole piece in each winding, and to isolate the two adjacent ones.
  • the positive pole piece and the negative pole piece that are close to each other in the winding to prevent short circuit of the positive and negative poles inside the battery.
  • the structure of the laminated body and the positional relationship of the various parts in the laminated body can be used by those skilled in the art by conventional technical means, and this application is not limited herein.
  • the layers in the laminate may be arranged in the order of a separator, a positive pole piece, a separator, and a negative pole piece.
  • each layer is wound in isolation.
  • the membrane is located at the innermost layer, and the negative pole piece is located at the outermost layer.
  • the reserved space is set inside the designated circle means that the pre-set is set between the innermost separator of the designated circle and the negative pole piece of the previous circle of the designated circle. Leave space.
  • the distance between the innermost layer of the bending section of the cell and the two points where the outermost layer has the greatest curvature can be understood as a bending section, the inner isolation film of the innermost layer of the cell is laminated with the outermost layer The distance between the two points with the largest curvature of the positive pole piece on the outside of the body.
  • the reserved space is set so that the line connecting the innermost layer of the bending section of the wound cell and the two points where the outermost layer has the largest curvature passes through the reserved space; the bending of the wound cell
  • the two points where the curvature of the innermost layer and the outermost layer of the segment are greatest can be the two points where the innermost layer and the outermost layer on the cell section are located on the center line 5 in the thickness direction of the cell;
  • the reserved space 3 may be arranged in the winding corner 4.
  • the thickness of the laminate can be understood as the sum of the thickness of the positive pole piece, the negative pole piece and the two separators.
  • the thickness of the flat section of the laminate can be considered There is no change before and after.
  • too large or too small reserved space 3 can not achieve the purpose of effectively inhibiting the lithium evolution and deformation of the pole piece. It is not limited to any theory. It can be considered that when g ⁇ m 1 N, it is not enough. To alleviate volume expansion, to suppress wrinkles and deformation; and when g ⁇ 1.87m 1 N, the space reserved inside the cell is too large, which causes the cell to deform, and the solid electrolyte interface (SEI) becomes worse, thereby affecting The degree of lithium insertion in the negative electrode and the diffusion rate of lithium ions cause the phenomenon of lithium evolution.
  • SEI solid electrolyte interface
  • a and g satisfy: 0.55m 1 N ⁇ 1000g/a ⁇ 1.90m 1 N; the inventor found in the research that when g and a satisfy the above proportional relationship, it can be obtained Better suppression of deformation and lithium precipitation.
  • the total number of winding turns N is usually an integer; in “at least one designated turn is in the range of N/4 to 3N/4", the "designated turn” is an integer turn, and the designated turn is in N/ In the range of 4 to 3N/4; when N/4 and 3N/4 are not integers, round up to the nearest whole number, and the value after rounding should be in the range of N/4 to 3N/4.
  • the number of the designated circles is 2 or 3, and the interval between two adjacent reserved spaces is 2-5 circle stacks; preferably, two adjacent ones The interval between the two reserved spaces is 2-3 turns of the laminated body; more preferably, the interval between two adjacent reserved spaces is 2 turns of the laminated body.
  • the inventor also discovered in research that in lithium-ion batteries, the cells will have different degrees of volume expansion during the process of lithium insertion.
  • the gram capacity is much higher than that of carbon-based anode materials in the prior art, so it is considered to be the most promising anode material for next-generation lithium-ion batteries; however, silicon-based anode materials have about 300% Volume expansion, the existing technology to prevent the deformation of the negative electrode material and inhibit the lithium evolution can hardly be applied to this kind of negative electrode material with high gram capacity and high expansion rate;
  • the unit volume capacity a (mAh/cm 3 ) of the pole piece and the distance between the innermost layer and the outermost layer of the bending section of the battery core at the maximum curvature g satisfies 0.55m 1 N ⁇ 1000g/a ⁇ 1.90m At 1 N, it can effectively reduce the probability of battery cell deformation and improve the problem of lithium evolution in the battery cell.
  • the battery of the present application includes a positive pole piece, a negative pole piece and a separator.
  • the negative pole piece includes a negative electrode current collector and a negative electrode coating.
  • the negative electrode coating is formed by coating a negative electrode material on the negative electrode current collector.
  • the negative electrode coating contains a negative electrode active material.
  • the negative electrode active material on the negative electrode piece contains a silicon-based material.
  • the silicon-based material used in this application is a material known in the art; it can be prepared according to the prior art or obtained through commercial channels.
  • the silicon-based material comprises nano-silicon particles. , Silicon oxide (SiOx, where 0.5 ⁇ x ⁇ 1.6), at least one of a silicon-carbon composite material or a silicon alloy; the particle size of the silicon-based material can be a conventional size in the field, in the first aspect of this application.
  • the average particle size of SiOx, silicon-carbon composite material or silicon alloy in the silicon-based material is 500 nm-30 ⁇ m; the average particle size of the nano silicon particles is less than 100 nm.
  • the silicon-based material may also contain elements such as lithium and magnesium.
  • the materials and preparation of the positive electrode sheet and the separator are not particularly limited, and they can be prepared by any method known to those skilled in the art or purchased from commercial sources.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode coating.
  • the positive electrode coating layer is formed by coating a positive electrode material on a positive electrode current collector, the positive electrode coating layer contains a positive electrode active material, and the positive electrode active material contains lithium cobaltate, lithium manganate, lithium iron phosphate, and nickel acid. At least one of lithium or lithium nickel cobalt oxide; the material of the isolation membrane is selected from at least one of polyethylene, polypropylene, and polyvinylidene fluoride.
  • the second aspect of the application provides the method for preparing the battery cell provided in the first aspect of the application, including:
  • a third aspect of the present application provides a lithium ion battery including the battery cell provided in the first aspect of the application, the lithium ion battery further includes an electrolyte and a packaging film, the battery is immersed in the electrolyte and packaged In the packaging film.
  • the electrolyte and packaging film used in this application are all materials known in the art; for example, the electrolyte can be prepared by the following method: in a dry argon environment, in propylene carbonate (PC), ethylene carbonate (EC) , Diethyl carbonate (DEC) is mixed with a weight ratio of 1:1:1 to the solvent solution, add lithium hexafluorophosphate (LiPF 6 ) and mix evenly.
  • the concentration of LiPF 6 is about 1.15mol/L, and then add 12wt% Fluorinated ethylene carbonate (FEC) is mixed uniformly to obtain an electrolyte.
  • the packaging film can be aluminum-plastic film; this application is not limited here.
  • the fourth aspect of the present application provides an electronic device, including the lithium ion battery provided in the third aspect of the present application.
  • the test temperature was 25° C., and the full batteries prepared in each example and comparative example were charged to 4.4V at a constant current of 0.7C, charged to 0.05C at a constant voltage, and discharged to 3.0V at 0.5C after standing for 5 minutes. Afterwards, a 0.7C charge/0.5C discharge cycle test was performed. After 10 cycles, the battery cell was removed and disassembled to observe the phenomenon of lithium precipitation.
  • the pole piece is golden yellow for non-lithium, and the pole piece is gray for lithium. And according to the area of the fully charged pole piece (gray) and the entire pole piece The ratio of the area to judge the degree of lithium extraction:
  • the positive pole piece is prepared by the following method:
  • the active material LiCoO 2 , conductive carbon black, and binder polyvinylidene fluoride (PVDF) are fully stirred and mixed in an N-methylpyrrolidone solvent system at a weight ratio of 96.7:1.7:1.6.
  • the solid content of the slurry is 30vol %, and then coated on the Al foil, dried, and cold pressed to obtain a positive pole piece.
  • a PE porous polymer film is used as the isolation membrane.
  • Negative electrode sheet were prepared: Example of a silicone material graphite embodiment (the SiOx, where 0.5 ⁇ x ⁇ 1.6) mixed at a certain proportion, to give capacity per unit volume of 619.8mAh / cm 3 of the mixed powder, the mixed powder, conductive Acetylene black and polyacrylic acid (PAA) are mixed thoroughly in a deionized water solvent system with a weight ratio of 95:1.2:3.8. The solid content of the slurry is 30vol%, and then the negative electrode material is coated on the Cu foil and baked Dry and cold press to obtain a negative pole piece; wherein the coating weight per unit area is 9.74 mg/cm 2 , and the coating thickness is 0.115 mm.
  • the coating weight per unit area is 9.74 mg/cm 2
  • the coating thickness is 0.115 mm.
  • Per unit volume mixed powder of EXAMPLE 14 was adjusted to 3000.0mAh / cm 3; a negative electrode coating weight per unit area becomes 2.279mg / cm 2; coating thickness becomes 0.0364mm; m 1 laminate thickness becomes 0.162 mm; the rest is the same as in Example 14.
  • Example 15 The capacity per unit volume in Example 15 was adjusted to the mixed powder 3000.0mAh / cm 3; a negative electrode coating weight per unit area becomes 2.279mg / cm 2; coating thickness becomes 0.0364mm; m 1 laminate thickness becomes 0.162 mm; the rest is the same as in Example 15.
  • Comparing Examples 1-3 and Comparative Examples 1-2, Examples 14, 15 and Comparative Examples 10 and 11 illustrate the same negative pole piece unit volume capacity, and by controlling different g values, that is, controlling the reservation Depending on the size of the space, battery cells have different lithium evolution situations. When m 1 N ⁇ g ⁇ 1.87m 1 N, none of the battery cells exhibit lithium evolution.
  • the size of the reserved space has a greater impact on the lithium evolution of the battery cell.
  • Different silicon content can provide different negative pole piece unit volume capacity, but it will also cause different degree of volume expansion. Therefore, different unit volume capacity should match different g value.
  • the bending section of the battery is set to reserve space When m 1 N ⁇ g ⁇ 1.87m 1 N, it can effectively alleviate the volume expansion, reduce the deformation probability of the pole piece, thereby improving the phenomenon of lithium precipitation in the battery; this improvement is at least suitable for the negative electrode unit volume capacity of 619mAh/cm 3 ⁇ 3000mAh/cm 3 anode material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Secondary Cells (AREA)

Abstract

La présente invention concerne une cellule de batterie au lithium-ion, comprenant des sections droites et des sections courbées. La cellule est formée par enroulement d'un stratifié comprenant une feuille d'électrode positive, une feuille d'électrode négative et un séparateur ; le nombre total de spires d'enroulement de la cellule est N, l'épaisseur du stratifié dans la section droite de la cellule est de m 1 millimètres, et un espace réservé est formé sur le côté interne d'au moins une spire spécifiée au niveau des sections courbées de la cellule, de telle sorte que la distance g entre deux points ayant les courbures maximales sur les couches interne et externe de la section courbée de la cellule satisfait m1N<g<1.87m1N ; la ou les spires spécifiées se trouvent dans une plage de N/4 à 3N/4 ; la capacité par volume de la feuille d'électrode négative est de a mAh/cm 3, et 619<a<3000. À l'aide de la cellule selon des modes de réalisation de la présente invention, un espace réservé approprié est formé au niveau de sections courbées de la cellule, de telle sorte que le phénomène de plissage ou de déformation provoqué par une expansion de la cellule peut être atténué, ce qui permet d'atténuer le problème de revêtement au lithium de la cellule.
PCT/CN2020/080042 2020-03-18 2020-03-18 Cellule de batterie au lithium-ion, son procédé de préparation et batterie au lithium-ion la comprenant WO2021184262A1 (fr)

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PCT/CN2020/080042 WO2021184262A1 (fr) 2020-03-18 2020-03-18 Cellule de batterie au lithium-ion, son procédé de préparation et batterie au lithium-ion la comprenant
CN202080094446.9A CN115039268A (zh) 2020-03-18 2020-03-18 一种锂离子电池的电芯、其制备方法及包含其的锂离子电池

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Cited By (9)

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CN114122315A (zh) * 2021-11-22 2022-03-01 宁德新能源科技有限公司 电化学装置和电子装置
CN114583289A (zh) * 2022-03-31 2022-06-03 珠海冠宇电池股份有限公司 一种锂离子电池
CN114824508A (zh) * 2022-05-17 2022-07-29 宁德新能源科技有限公司 电化学装置及包含该电化学装置的电子装置
CN115036587A (zh) * 2022-08-15 2022-09-09 中创新航科技股份有限公司 单体电池、电池组及用电设备
CN115832186A (zh) * 2022-07-11 2023-03-21 宁德时代新能源科技股份有限公司 电芯组件、电池单体、电池以及用电装置
CN116190806A (zh) * 2023-02-28 2023-05-30 深圳市康胜新能源产品有限公司 一种磷酸铁锂电芯以及电芯加工工艺
CN116914277A (zh) * 2023-09-12 2023-10-20 厦门海辰储能科技股份有限公司 一种电池单体、电池包及其用电装置
CN117706386A (zh) * 2024-02-05 2024-03-15 苏州易来科得科技有限公司 锂电池正负极嵌锂系数上下限的计算方法和装置
WO2024098175A1 (fr) * 2022-11-07 2024-05-16 宁德时代新能源科技股份有限公司 Batterie secondaire, son procédé de préparation et dispositif électrique

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CN116914228B (zh) * 2023-09-13 2024-04-12 厦门海辰储能科技股份有限公司 电芯、电池和用电设备

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
CN114122315A (zh) * 2021-11-22 2022-03-01 宁德新能源科技有限公司 电化学装置和电子装置
CN114583289A (zh) * 2022-03-31 2022-06-03 珠海冠宇电池股份有限公司 一种锂离子电池
CN114824508A (zh) * 2022-05-17 2022-07-29 宁德新能源科技有限公司 电化学装置及包含该电化学装置的电子装置
CN115832186A (zh) * 2022-07-11 2023-03-21 宁德时代新能源科技股份有限公司 电芯组件、电池单体、电池以及用电装置
CN115036587A (zh) * 2022-08-15 2022-09-09 中创新航科技股份有限公司 单体电池、电池组及用电设备
WO2024098175A1 (fr) * 2022-11-07 2024-05-16 宁德时代新能源科技股份有限公司 Batterie secondaire, son procédé de préparation et dispositif électrique
CN116190806A (zh) * 2023-02-28 2023-05-30 深圳市康胜新能源产品有限公司 一种磷酸铁锂电芯以及电芯加工工艺
CN116914277A (zh) * 2023-09-12 2023-10-20 厦门海辰储能科技股份有限公司 一种电池单体、电池包及其用电装置
CN116914277B (zh) * 2023-09-12 2024-01-26 厦门海辰储能科技股份有限公司 一种电池单体、电池包及其用电装置
CN117706386A (zh) * 2024-02-05 2024-03-15 苏州易来科得科技有限公司 锂电池正负极嵌锂系数上下限的计算方法和装置
CN117706386B (zh) * 2024-02-05 2024-05-07 苏州易来科得科技有限公司 锂电池正负极嵌锂系数上下限的计算方法和装置

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