WO2021057688A1 - 一种异步加热延压装置、大宽幅超薄金属锂箔及其制备方法和应用 - Google Patents

一种异步加热延压装置、大宽幅超薄金属锂箔及其制备方法和应用 Download PDF

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WO2021057688A1
WO2021057688A1 PCT/CN2020/116658 CN2020116658W WO2021057688A1 WO 2021057688 A1 WO2021057688 A1 WO 2021057688A1 CN 2020116658 W CN2020116658 W CN 2020116658W WO 2021057688 A1 WO2021057688 A1 WO 2021057688A1
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Prior art keywords
lithium
unwinding
belt
roller
heating
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PCT/CN2020/116658
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English (en)
French (fr)
Inventor
李文俊
李永伟
向晋
俞会根
何亚菲
侯宝鹏
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北京卫蓝新能源科技有限公司
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Priority to EP20867180.0A priority Critical patent/EP4037003A1/en
Priority to JP2022519376A priority patent/JP7466635B2/ja
Priority to US17/763,357 priority patent/US20220352491A1/en
Priority to KR1020227013530A priority patent/KR20220070253A/ko
Publication of WO2021057688A1 publication Critical patent/WO2021057688A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D13/00—Corrugating sheet metal, rods or profiles; Bending sheet metal, rods or profiles into wave form
    • B21D13/04—Corrugating sheet metal, rods or profiles; Bending sheet metal, rods or profiles into wave form by rolling
    • B21D13/045—Corrugating sheet metal, rods or profiles; Bending sheet metal, rods or profiles into wave form by rolling the corrugations being parallel to the feeding movement
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B21B2001/225—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length by hot-rolling
    • 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 invention belongs to the technical field of ultra-thin lithium foil, and in particular relates to an asynchronous heating and rolling device, a large-width ultra-thin metal lithium foil, and a preparation method and application thereof.
  • Lithium-ion batteries are widely used in consumer electronics and electric vehicles due to their high energy density, long service life, and green pollution-free advantages.
  • SEI film solid electrolyte membrane
  • the replenishment process of lithium-ion battery pole pieces is a key technology to improve the capacity of lithium batteries, and its core lies in rolling and laminating.
  • Calendering is a process in which a lithium belt of 0.25 mm to 2 mm is rolled to form a lithium film of 0.002 mm to 0.006 mm and attached to the traction film.
  • the purpose of the present invention is to provide an asynchronous heating and rolling device, a large-width ultra-thin metal lithium foil, and a preparation method and application thereof.
  • the device can prepare a large-width ultra-thin lithium belt with a uniform thickness.
  • the invention provides an asynchronous heating and rolling device for preparing large-width ultra-thin metal lithium foil in a short process, which includes a pulling substrate unwinding unit for unwinding and pulling the substrate;
  • Lithium belt unwinding unit used to unwind the lithium belt
  • Lithium belt pre-shaping unit Lithium belt pre-shaping unit
  • Asynchronous heating and calendering unit includes a first calender roll, a second calender roll, and a heating box; the heating box is used to heat the first calender roll; the first calender roll pair is drawn The substrate is heated; the axes of the first and second rolling rollers are parallel and opposite to each other, so that the traction substrate and the lithium belt are combined into a composite belt;
  • the rewinding unit is used to rewind the composite tape.
  • the surface of the second calender roll is covered with a ceramic layer or a polymer layer.
  • the ceramic layer includes one or more of alumina, zirconia, chromium oxide, and composite ceramic coating;
  • the polymer coating includes one or more of polysiloxane, long-chain alkanes, and paraffin wax. kind.
  • the lithium belt unwinding unit includes a lithium belt unwinding roller, a first auxiliary guide roller, a first tension detection roller and a speed measuring roller which are arranged in sequence;
  • the traction substrate unwinding unit includes a substrate unwinding roller, a second auxiliary guide roller, a first correction sensor, a third auxiliary guide roller, and a fourth auxiliary guide roller that are sequentially arranged;
  • the lithium belt pre-shaping unit includes a second correction sensor and a shaping roller arranged oppositely arranged in sequence;
  • the winding unit includes a second tension detection roller, a third correction sensor and a composite belt winding roller which are sequentially arranged.
  • the traction substrate is selected from stainless steel foil, copper foil, steel foil or iron foil.
  • the present invention provides a method for preparing large-width ultra-thin lithium foil using the asynchronous heating and rolling device described in the above technical scheme, which includes the following steps:
  • the lithium belt After unwinding and pre-shaping, the lithium belt is asynchronously heated and calendered in the gap between the first calender roll and the second calender roll with the unrolled traction substrate, and then rewinded to obtain a composite ribbon;
  • the temperature of the asynchronous heating and calendering treatment is 50-250°C; the rotation speed ratio of the first calender roll and the second calender roll is 1:1.1-8.
  • the unwinding speed of the lithium belt is 0.1 to 3 m/min; the unwinding speed of the pulling substrate is 0.1-20 m/min.
  • the tension during the unwinding of the lithium belt is 5-100N; the deviation correction accuracy of the pulling substrate and the unwinding of the lithium belt are both ⁇ 0.2 mm.
  • the present invention provides a large-width ultra-thin lithium foil prepared by the method described in the above technical scheme;
  • the width of the lithium foil is 1 to 600 mm; the thickness of the lithium foil is 1 to 20 ⁇ m.
  • the present invention provides a battery including the large-width ultra-thin lithium foil described in the above technical solution.
  • the invention provides an asynchronous heating and rolling device for preparing large-width ultra-thin metal lithium foil in a short process, which includes a pulling substrate unwinding unit for unwinding the pulling substrate; a lithium belt unwinding unit for unwinding Lithium belt; asynchronous heating and calendering unit, the asynchronous heating and calendering unit includes a first calender roll, a second calender roll and a heating box; the heating box is used to heat the first calender roll; the first calender The roller heats the traction substrate; the axis of the first and second scalping rollers are parallel and opposite to each other, so that the traction substrate and the lithium belt are combined into a composite belt; the winding unit is used to wind the composite belt .
  • the device pulls the base material unwinding unit to unwind the base material. After the lithium belt unwinding unit unwinds the lithium belt, it is pre-shaped and transported to the first rolling roll and the second rolling roll for compounding to obtain a composite belt. Then it is rewinded by the composite belt rewinding unit.
  • the device can produce a large, wide and ultra-thin metal lithium foil with uniform thickness by setting a heating box and asynchronous first and second rolling rolls; the lithium foil has a high primary effect when applied to batteries.
  • the experimental results show that the width of the lithium foil is 1 ⁇ 600mm; the thickness of the lithium foil is 1 ⁇ 20 ⁇ m; the first effect of the battery is as high as 98%; 150 points in the lateral direction of the lithium belt are used as test points, and the relative error of the effective thickness is 0 ⁇ 3%; 30 points in the longitudinal direction are used as test points, and the relative error of the effective thickness is 0 ⁇ 2%.
  • FIG. 1 is a schematic diagram of the structure of an asynchronous heating and rolling device for preparing large-width ultra-thin metal lithium foil in a short process provided by the present invention.
  • the present invention provides an asynchronous heating and rolling device for preparing large-width ultra-thin metal lithium foil in a short process, which includes a pulling substrate unwinding unit for unwinding and pulling the substrate;
  • Lithium belt unwinding unit used to unwind the lithium belt
  • Lithium belt pre-shaping unit Lithium belt pre-shaping unit
  • Asynchronous heating and calendering unit includes a first calender roll, a second calender roll, and a heating box; the heating box is used to heat the first calender roll; the first calender roll pair is drawn The substrate is heated; the axes of the first and second rolling rollers are parallel and opposite to each other, so that the traction substrate and the lithium belt are combined into a composite belt;
  • the rewinding unit is used to rewind the composite tape.
  • Figure 1 is a schematic diagram of the asynchronous heating and rolling device for preparing large-width ultra-thin metal lithium foil in a short process provided by the present invention, in which D-lithium tape unwinding unit, E-pulling substrate unwinding unit, F -Lithium belt pre-shaping unit, H-asynchronous heating calender unit, G-winding unit.
  • lithium belt unwinding unit (D) 1-lithium belt unwinding roller, 2-first auxiliary guide roller, 3-tension detection roller 1, 4-speed measuring roller;
  • traction substrate unwinding unit (E) 8- traction substrate unwinding roller, 9-second auxiliary guide roller, 10-first correction sensor, 11-third auxiliary guide roller, 12-fourth auxiliary guide roller;
  • P-traction substrate S-lithium belt
  • Z-composite belt ie, traction substrate and lithium belt composite
  • the present invention uses the calender roller near the lithium ribbon side in the asynchronous heating calender unit , That is, the surface coating treatment of the second calender roll; preferably the ceramic layer or the polymer layer is coated.
  • the ceramic layer includes one or more of alumina, zirconia, chromium oxide and composite ceramic coating; the polymer coating includes one or more of polysiloxane, long-chain alkanes and paraffin wax kind.
  • the traction substrate is preferably selected from stainless steel foil, copper foil, steel foil or iron foil.
  • the lithium belt unwinding unit includes a lithium belt unwinding roller, a first auxiliary guide roller, a first tension detection roller and a speed measuring roller which are arranged in sequence;
  • the traction substrate unwinding unit includes a substrate unwinding roller, a second auxiliary guide roller, a first correction sensor, a third auxiliary guide roller, and a fourth auxiliary guide roller that are arranged in sequence;
  • the lithium belt pre-shaping unit includes a second correction sensor and a shaping roller arranged oppositely arranged in sequence;
  • the winding unit includes a second tension detection roller, a third correction sensor and a composite belt winding roller which are sequentially arranged.
  • the speed difference between the first calender roll and the second calender roll are set at their respective speeds in the asynchronous heating calender unit to make the two asynchronous, so as to ensure that the lithium belt is not only subjected to the first
  • the radial force of the calender roll and the second calender roll and the tangential force of the first calender roll and the second calender roll make it easier to realize the ultra-thin lithium belt.
  • the heating box can heat the first calender roll to provide heat for drawing the base material and the lithium ribbon during rolling and composite, so that the solid metal lithium ribbon maintains a semi-solid state during calendering, thereby making it easier to achieve ultra-thin lithium ribbon .
  • the substrate unwinding unit provides the attachment of the ultra-thin lithium belt after rolling and the transported substrate;
  • the lithium belt unwinding mechanism provides and transports the lithium belt to be rolled;
  • the pre-shaping unit flattens the lithium belt from both sides before the lithium belt enters the asynchronous heating and rolling unit, thereby improving the thickness consistency of the lithium belt, and reducing the adverse effect of the fluctuation of the thickness of the lithium belt on the rolling effect;
  • the lithium ribbon pre-shaping mechanism is arranged upstream of the asynchronous heating and calendering unit and used to flatten the lithium ribbon from both sides.
  • the lithium ribbon passes through the pre-shaping unit and then passes through the first calender roller and the second calender in the asynchronous heating calender unit. Roll gap between rolls.
  • the specific process of using the above asynchronous heating and rolling device includes:
  • Step 2 Adjust the roll gap
  • the tangential force and heat are applied to the calendered lithium belt to obtain ultra-thin metallic lithium.
  • the present invention provides a method for preparing large-width ultra-thin lithium foil using the asynchronous heating and rolling device described in the above technical scheme, which includes the following steps:
  • the lithium belt After unwinding and pre-shaping, the lithium belt is asynchronously heated and calendered in the gap between the first calender roll and the second calender roll with the unrolled traction base material, and then rewinded to obtain a composite ribbon;
  • the temperature of the asynchronous heating and calendering treatment is 50-250°C; the rotation speed ratio of the first calender roll and the second calender roll is 1:1.1-8.
  • the present invention heats the first calender roll through a heating box, and combines the asynchronous of the first calender roll and the second calender roll, that is, the speed is different, so that the lithium belt is ultra-thin and has excellent performance, such as the prepared
  • the battery has a high first effect.
  • the temperature of the asynchronous heating and calendering treatment is 50-250°C; in a specific embodiment, the temperature of the asynchronous heating and calendering treatment is 80°C or 120°C.
  • the pressure of the asynchronous heating and calendering treatment is preferably 3-6T; in a specific embodiment, the pressure of the asynchronous heating and calendering treatment is 4T or 5T.
  • the rotation speed ratio of the first rolling roll and the second rolling roll is 1:1.1-8.
  • the speed of the first calender roll is preferably 1-5 m/min, and the speed of the second calender roll is preferably 1-10 m/min. In a specific embodiment, the speed of the first calender roll is 3m/min; the speed of the second calender roll is 1.5m/min or 2m/min.
  • the unwinding speed of the lithium belt is 0.1-3m/min; the unwinding speed of the pulling substrate is 0.1-20m/min.
  • the tension during the unwinding of the lithium belt is 5-100N; the deviation correction accuracy of the pulling substrate and the unwinding of the lithium belt are preferably ⁇ 0.2 mm.
  • the present invention provides a large-width ultra-thin lithium foil prepared by the method described in the above technical scheme;
  • the width of the lithium foil is 1 to 600 mm; the thickness of the lithium foil is 1 to 20 ⁇ m.
  • the width of the lithium foil is preferably 80 to 100 mm.
  • the present invention provides a battery including the large-width ultra-thin lithium foil described in the above technical solution.
  • the above-mentioned ultra-thin lithium foil is preliminated on the SiOC pole piece, and the battery is assembled with the NCA.
  • a battery made of the large-width ultra-thin lithium foil described in the above technical solution has a higher first cycle efficiency, that is, the first effect.
  • an asynchronous heating rolling device provided by the present invention, a large-width ultra-thin metal lithium foil and its preparation method and application will be described in detail below in conjunction with examples, but they cannot be understood as protecting the present invention. Limitation of the scope.
  • the drawing substrate (P) is a 10 ⁇ m copper foil
  • the relative distance between the calender roll (A) and the calender roll (B) is adjusted to 11 ⁇ m
  • the heating box temperature is adjusted to 120°C.
  • Heat the calender roll B adjust the speed of the calender roll (A) to 1.5m/min, the speed of the calender roll (B) to 3m/min, the pressure between the calender rolls is 5T, and pass through the winding unit
  • the continuous winding of (G) results in a composite belt (Z) with a thickness of 20 ⁇ m and a width of 80 mm, among which the effective thickness of the lithium belt is 10 ⁇ m.
  • the ultra-thin lithium tape prepared in Example 1 is preliminated on the SiOC pole piece, and the battery is assembled with the NCA.
  • the test result is: the first cycle efficiency is 98%. And without pre-lithium SiOC-NCA battery, the first efficiency is only 76%.
  • Randomly select a 50cm section of lithium belt in the middle take one point every 1cm in the longitudinal direction to measure the thickness, measure the thickness of the two sides and the middle of the lithium belt, a total of 150 points; measure the thickness on both sides and the middle of the belt, measure one point every 1cm, total Measure 24 points.
  • the traction substrate (P) is a 10 ⁇ m stainless steel foil.
  • the relative distance between the calender roll (A) and the calender roll (B) is adjusted to 22 ⁇ m, and the heating box temperature is adjusted to 80°C.
  • Heat the calender roll B adjust the speed of the calender roll (A) to 2m/min, the speed of the calender roll (B) to 3m/min, the pressure between the calender rolls is 4T, and pass the winding unit ( G) is continuously reeled to obtain a composite belt (Z) with a thickness of 30 ⁇ m and a width of 100 cm, in which the effective thickness of the lithium belt is 20 ⁇ m.
  • the ultra-thin lithium belt prepared in Example 2 is preliminated on the SiOC pole piece, and the battery is assembled with the NCA.
  • the test result is: the first cycle efficiency is 98%.
  • Randomly select a 50cm section of lithium belt in the middle take one point every 1cm in the longitudinal direction to measure the thickness, measure the thickness of both sides and the middle of the lithium belt, a total of 150 points; measure the thickness of both sides and the middle longitudinally, measure one point every 1cm, total Measure 30 points.
  • the present invention provides an asynchronous heating and rolling device for preparing large-width ultra-thin metal lithium foil in a short process, including a pulling substrate unwinding unit for unwinding the pulling substrate; lithium tape unwinding A unit for unwinding the lithium belt; an asynchronous heating and calendering unit, the asynchronous heating and calendering unit includes a first calender roll, a second calender and a heating box; the heating box is used to heat the first calender roll; The first calender roller heats the traction substrate; the axis of the first calender roller and the second calender roller are parallel and opposite to each other, so that the traction substrate and the lithium belt are combined into a composite belt; a winding unit, Used to rewind composite tape.
  • the device can produce a large and wide ultra-thin metal lithium foil with uniform thickness by setting a heating box and asynchronous first and second rolling rolls; the lithium foil has a high primary effect when applied to batteries.
  • the experimental results show that: the width of the lithium foil is 1 ⁇ 600mm; the thickness of the lithium foil is 1 ⁇ 20 ⁇ m; the first effect of the battery is as high as 98%; 150 points in the lateral direction of the lithium belt are used as test points, and the relative error of the effective thickness is 0 ⁇ 3%; 30 points in the longitudinal direction are used as test points, and the relative error of the effective thickness is 0 ⁇ 2%.

Abstract

一种异步加热延压装置、大宽幅超薄金属锂箔及其制备方法和应用，异步加热延压装置包括牵引基材放卷单元（E），用来放卷牵引基材（P）；锂带放卷单元（D），用来放卷锂带（S）；异步加热压延单元（Ｈ），异步加热压延单元（Ｈ）中包括第一延压辊（Ｂ）、第二延压辊（Ａ）和加热箱（Ｃ）；所述加热箱（Ｃ）用来加热第一延压辊（Ｂ）；所述第一延压辊（Ｂ）对牵引基材（Ｐ）进行加热；所述第一延压辊（Ｂ）和第二延压辊（Ａ）轴线平行，对向设置，使牵引基材（Ｐ）和锂带（Ｓ）复合为复合带（Ｚ）；收卷单元（Ｇ），用来收卷复合带（Ｚ）。该装置通过设置加热箱（Ｃ）和异步的第一延压辊（Ｂ）和第二延压辊（Ａ），能够制得厚度均一的大宽幅超薄金属锂箔；该锂箔应用在电池中具有较高的首效。锂箔的宽度为1～600mm；所述锂箔的厚度为1～20μm；电池的首效高达98％。

Description

一种异步加热延压装置、大宽幅超薄金属锂箔及其制备方法和应用
本申请要求于2019年09月25日提交中国专利局、申请号为201910911287.6、发明名称为“一种异步加热延压装置、大宽幅超薄金属锂箔及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于超薄锂箔技术领域，尤其涉及一种异步加热延压装置、大宽幅超薄金属锂箔及其制备方法和应用。
背景技术
锂离子电池由于能量密度高、使用寿命长、绿色无污染等优势被广泛应用于消费类电子产品和电动汽车领域。然而在锂电池的首次充放电过程中都会由于固体电解质膜(SEI膜)的形成而消耗部分锂，造成正极材料锂的损失，且此不可逆的首次容量的损失直接导致电池容量的损失。目前，锂离子电池极片的补锂工艺是提高锂电池容量的关键技术，其核心在于压延与覆合。压延即是将0.25mm～2mm的锂带通过辊压形成0.002mm～0.006mm的锂膜，并使其附着于牵引膜上的一种工艺方法。
现有的补锂工艺，在压延锂带的过程中，当锂带来料的厚度波动较大(≥±10μm)时，特别是当锂带幅宽较大(150mm以上)时，锂带在入料过程中宽度方向所受的张力不均，通常是两边大中间小，使得锂带宽度方向上的形变量不一致(厚度不均，中间厚两边薄)，因此，在压辊高速运转时，锂带来料厚度的波动、锂带宽度方向张力的不一致以及锂带宽度方向形变不均匀等因素容易导致锂带中间部位堆积在辊压入料处并形成锂堆积，锂堆积越积越多且难以消除，严重影响锂带正常入料，降低了锂带压延的厚度一致性，导致无法连续生产，造成物料浪费、产能降低。另外，传统的压延对辊压机的要求较高，传统的单纯的辊压根本无法实现将锂带辊压到2μm～6μm的厚度，即使能够实现也需要其他辅助材料，但辅助材料价格昂贵近一步提高锂带的成本且不能完全得到成分单一的金属锂带从而严重影响其性能。
发明内容
有鉴于此，本发明的目的在于提供一种异步加热延压装置、大宽幅超薄金属锂箔及其制备方法和应用，该装置能够制备得到厚度均一的大宽幅超薄锂带。
本发明提供了一种短流程制备大宽幅超薄金属锂箔的异步加热延压装置，包括牵引基材放卷单元，用来放卷牵引基材；
锂带放卷单元，用来放卷锂带；
锂带预整形单元；
异步加热压延单元，所述异步加热压延单元中包括第一延压辊、第二延压辊和加热箱；所述加热箱用来加热第一延压辊；所述第一延压辊对牵引基材进行加热；所述第一延压辊和第二延压辊轴线平行，对向设置，使牵引基材和锂带复合为复合带；
收卷单元，用来收卷复合带。
优选地，第二延压辊的表面包覆陶瓷层或聚合物层。所述陶瓷层包括氧化铝、氧化锆、氧化铬、复合物陶瓷涂层中的一种或多种；所述聚合物涂层包括聚硅氧烷、长链烷烃、石蜡中的一种或多种。
优选地，所述锂带放卷单元中包括依次设置的锂带放卷辊、第一辅助导辊、第一张力检测辊和测速辊；
所述牵引基材放卷单元中包括依次设置的基材放卷辊、第二辅助导辊、第一纠偏传感器、第三辅助导辊和第四辅助导辊；
所述锂带预整形单元中包括依次设置的第二纠偏传感器和对向设置的整形辊；
所述收卷单元中包括依次设置的第二张力检测辊、第三纠偏传感器和复合带收卷辊。
优选地，所述牵引基材选自不锈钢箔，铜箔，钢箔或铁箔。
本发明提供了一种采用上述技术方案所述异步加热延压装置制备大宽幅超薄锂箔的方法，包括以下步骤：
锂带经放卷和预整形后与放卷的牵引基材在第一延压辊和第二延压辊之 间的辊缝中异步加热压延处理，收卷，得到复合带；
所述异步加热压延处理的温度为50～250℃；所述第一延压辊和第二延压辊的转速比为1:1.1～8。
优选地，锂带放卷的速度为0.1～3m/min；牵引基材放卷的速度为0.1～20m/min。
优选地，所述锂带放卷时的张力为5～100N；牵引基材和锂带放卷时的纠偏精度均为±0.2mm。
本发明提供了一种大宽幅超薄锂箔，由上述技术方案所述方法制得；
所述锂箔的宽度为1～600mm；所述锂箔的厚度为1～20μm。
本发明提供了一种电池，包括上述技术方案所述的大宽幅超薄锂箔。
本发明提供了一种短流程制备大宽幅超薄金属锂箔的异步加热延压装置，包括牵引基材放卷单元，用来放卷牵引基材；锂带放卷单元，用来放卷锂带；异步加热压延单元，所述异步加热压延单元中包括第一延压辊、第二延压辊和加热箱；所述加热箱用来加热第一延压辊；所述第一延压辊对牵引基材进行加热；所述第一延压辊和第二延压辊轴线平行，对向设置，使牵引基材和锂带复合为复合带；收卷单元，用来收卷复合带。该装置牵引基材放卷单元放卷基材，锂带放卷单元放卷锂带经预整形后，同时输送至第一延压辊和第二延压辊之间进行复合，得到复合带，再通过复合带收卷单元收卷。该装置通过设置加热箱和异步的第一延压辊和第二延压辊，能够制得厚度均一的大宽幅超薄金属锂箔；该锂箔应用在电池中具有较高的首效。实验结果表明：锂箔的宽度为1～600mm；所述锂箔的厚度为1～20μm；电池的首效高达98％；锂带横向上150个点作为测试点，有效厚度的相对误差为0～3％；纵向上30个点作为测试点，有效厚度的相对误差为0～2％。
附图说明
图1为本发明提供的短流程制备大宽幅超薄金属锂箔的异步加热延压装置结构示意图。
具体实施方式
本发明提供了一种短流程制备大宽幅超薄金属锂箔的异步加热延压装置， 包括牵引基材放卷单元，用来放卷牵引基材；
锂带放卷单元，用来放卷锂带；
锂带预整形单元；
异步加热压延单元，所述异步加热压延单元中包括第一延压辊、第二延压辊和加热箱；所述加热箱用来加热第一延压辊；所述第一延压辊对牵引基材进行加热；所述第一延压辊和第二延压辊轴线平行，对向设置，使牵引基材和锂带复合为复合带；
收卷单元，用来收卷复合带。
参见图1，图1为本发明提供的短流程制备大宽幅超薄金属锂箔的异步加热延压装置结构示意图，其中D-锂带放卷单元、E-牵引基材放卷单元、F-锂带预整形单元、H-异步加热压延单元、G-收卷单元。
锂带放卷单元中(D)中1-锂带放卷辊、2-第一辅助导辊、3-张力检测辊1、4-测速辊；
牵引基材放卷单元(E)中8-牵引基材放卷辊、9-第二辅助导辊、10-第一纠偏传感器、11-第三辅助导辊、12-第四辅助导辊；
锂带预整形单元(F)中5-第二纠偏传感器、6-整形辊1、7-整形辊2；
异步加热压延单元(H)中A-第二延压辊、B-第一延压辊、C-加热箱；
收卷单元(G)中13-第二张力检测辊、14-第三纠偏传感器、15-复合带收卷辊；
P-牵引基材、S-锂带、Z-复合带(即牵引基材和锂带复合)。
为了保证锂带不附着于延压辊表面造成延压辊表面污染、锂带材料的浪费以及后续对复合带厚度均匀性的影响，本发明在异步加热压延单元中靠近锂带侧的延压辊，即第二延压辊的表面包覆处理；优选包覆陶瓷层或聚合物层。所述陶瓷层包括氧化铝、氧化锆、氧化铬和复合物陶瓷涂层中的一种或多种；所述聚合物涂层包括聚硅氧烷、长链烷烃和石蜡中的一种或多种。
在本发明中，所述牵引基材优选选自不锈钢箔，铜箔，钢箔或铁箔。
在本发明中，所述锂带放卷单元中包括依次设置的锂带放卷辊、第一辅助导辊、第一张力检测辊和测速辊；
所述牵引基材放卷单元中包括依次设置的基材放卷辊、第二辅助导辊、第 一纠偏传感器、第三辅助导辊和第四辅助导辊；
所述锂带预整形单元中包括依次设置的第二纠偏传感器和对向设置的整形辊；
所述收卷单元中包括依次设置的第二张力检测辊、第三纠偏传感器和复合带收卷辊。
在本发明中，所述第一延压辊和第二延压辊的速度差在异步加热压延单元中分别设定各自的速度，使二者异步，从而保证在压延时锂带不仅受到第一延压辊和第二延压辊径向的力而且受到第一延压辊和第二延压辊的切向力更容易将锂带实现超薄。
所述加热箱能够对第一延压辊进行加热，为牵引基材和锂带延压复合时提供热量，从而使得固态金属锂带在压延时维持半固态状态从而更容易将锂带实现超薄。
所述基材放卷单元提供压延后超薄锂带的依附以及运送的基材；锂带放卷机构提供、输送待压延的锂带；
所述预整形单元，在锂带进入异步加热压延单元之前从两侧压平锂带，从而改善锂带的厚度一致性，以降低锂带厚度波动对压延效果的不利影响；
所述锂带预整形机构设置在异步加热压延单元的上游并用于从两侧压平锂带，锂带穿过预整形单元后穿过异步加热压延单元中第一延压辊和第二延压辊之间的辊缝。
具体的，采用上述异步加热延压装置的具体过程包括：
将牵引基材(P)通过基材放卷辊(8)、第二辅助导辊(9)、第一纠偏传感器(10)、第三辅助导辊(11)、辅助导辊4(12)以及第二延压辊(A)和第一延压辊(B)之间的辊缝进行事先的穿带，最后将牵引基材(P)的头端固定到收卷辊(15)上并使牵引基材(P)处于张紧状态；接着将锂带(S)通过锂带放卷辊(1)、辅助导辊1(2)、张力检测辊1(3)、测速辊(4)及锂带预整形机构(E)中的纠偏传感器2(5)、整形辊1(6)和整形辊2(7)间的辊缝，最后穿过延压辊(A)和加热延压辊(B)之间的辊缝，接着将锂带(S)粘贴到牵引基材(P)上，并使锂带处于张紧状态；
步骤二:调辊缝
调整第二延压辊(A)和第一延压辊(B)之间的相对距离，即预期得到超薄锂带的厚度；
步骤三:加热
通过调整加热箱的温度实现对第二延压辊(A)以及牵引基材(P)的加热；
步骤四:调速
通过调整第二延压辊(A)和第一延压辊(B)的相对速度，对延压的锂带施加切向力同热量的配合从而得到超薄金属锂。
本发明提供了一种采用上述技术方案所述异步加热延压装置制备大宽幅超薄锂箔的方法，包括以下步骤：
锂带经放卷和预整形后与放卷的牵引基材在第一延压辊和第二延压辊之间的辊缝中异步加热压延处理，收卷，得到复合带；
所述异步加热压延处理的温度为50～250℃；所述第一延压辊和第二延压辊的转速比为1:1.1～8。
本发明通过加热箱对第一延压辊加热，再结合第一延压辊和第二延压辊的异步，也就是速度不同，使得锂带实现超薄，且具有优异的性能，如制备的电池具有较高的首效。
在本发明中，所述异步加热压延处理的温度为50～250℃；在具体实施例中，所述异步加热压延处理的温度为80℃或120℃。
所述异步加热压延处理的压力优选为3～6T；在具体实施例中，所述异步加热压延处理的压力为4T或5T。
所述第一延压辊和第二延压辊的转速比为1:1.1～8。所述第一延压辊速度优选为1-5m/min，第二延压辊速度优选为1～10m/min。在具体实施例中，所述第一延压辊的速度为3m/min；所述第二延压辊的速度为1.5m/min或2m/min。
在本发明中，锂带放卷的速度为0.1～3m/min；牵引基材放卷的速度为0.1～20m/min。所述锂带放卷时的张力为5～100N；牵引基材和锂带放卷时的纠偏精度均优选为±0.2mm。
本发明提供了一种大宽幅超薄锂箔，由上述技术方案所述方法制得；
所述锂箔的宽度为1～600mm；所述锂箔的厚度为1～20μm。
所述锂箔的宽度优选为80～100mm。
本发明提供了一种电池，包括上述技术方案所述的大宽幅超薄锂箔。
本发明将上述超薄锂箔对SiOC极片进行预锂，与NCA进行组装电池。
采用上述技术方案所述的大宽幅超薄锂箔制作的电池具有较高的首次循环效率，即首效。
为了进一步说明本发明，下面结合实施例对本发明提供的一种异步加热延压装置、大宽幅超薄金属锂箔及其制备方法和应用进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
将牵引基材(P)通过基材放卷辊(8)、第二辅助导辊(9)、第一纠偏传感器(10)、第三辅助导辊(11)、辅助导辊4(12)以及第二延压辊(A)和第一延压辊(B)之间的辊缝进行事先的穿带，最后将牵引基材(P)的头端固定到收卷辊(15)上并使牵引基材(P)处于张紧状态；接着将锂带(S)通过锂带放卷辊(1)、辅助导辊1(2)、张力检测辊1(3)、测速辊(4)及锂带预整形机构(F)中的纠偏传感器2(5)、整形辊1(6)和整形辊2(7)间的辊缝，最后穿过延压辊(A)和加热延压辊(B)之间的辊缝，接着将锂带(S)粘贴到牵引基材(P)上，并使锂带处于张紧状态；
其中，牵引基材(P)为10μm铜箔，穿带完成后，然后调整延压辊(A)和延压辊(B)之间的相对距离为11μm，将加热箱温度调整为120℃，对延压辊B进行加热，调整延压辊(A)的速度为1.5m/min，延压辊(B)的速度为3m/min，延压辊之间的压力为5T，通过收卷单元(G)的不断收卷，得到复合带(Z)的厚度为20μm，宽度为80mm，其中锂带的有效厚度为10μm。
本发明将实施例1制备的超薄锂带对SiOC极片进行预锂，与NCA进行组装电池。测试结果为：首次循环效率为98％。而不预锂SiOC-NCA电池首效仅为76％。
随机选取中部一段50cm的锂带，纵向每隔1cm左右取一个点测量厚度，测量锂带两边和中间的厚度，共150个点；横向测量两边和中间的厚度，每隔1cm测量一个点，一共测量24个点。
表1本发明实施例1提供的锂带纵向上不同点的有效厚度测试结果
Figure PCTCN2020116658-appb-000001
Figure PCTCN2020116658-appb-000002
表2本发明实施例1提供的锂带横向上不同点的有效厚度测试结果
Figure PCTCN2020116658-appb-000003
Figure PCTCN2020116658-appb-000004
实施例2
将牵引基材(E)通过基材放卷辊(8)、第二辅助导辊(9)、第一纠偏传感器(10)、第三辅助导辊(11)、辅助导辊4(12)以及第一延压辊(A)和第二延压辊(B)之间的辊缝进行事先的穿带，最后将牵引基材(P)的头端固定到收卷辊(15)上并使牵引基材(P)处于张紧状态；接着将锂带(S)通过锂带放卷辊(1)、辅助导辊1(2)、张力检测辊1(3)、测速辊(4)及锂带预整形机构(F)中的纠偏传感器2(5)、整形辊1(6)和整形辊2(7)间的辊缝，最后穿过延压辊(A)和加热延压辊(B)之间的辊缝，接着将锂带(S)粘贴到牵引基材(P)上，并使锂带处于张紧状态；
其中，牵引基材(P)为10μm不锈钢箔，穿带完成后，然后调整延压辊(A)和延压辊(B)之间的相对距离为22μm，将加热箱温度调整为80℃，对延压辊B进行加热，调整延压辊(A)的速度为2m/min，延压辊(B)的速度为3m/min，延压辊之间的压力为4T，通过收卷单元(G)的不断收卷，得到复合带(Z)的厚度为30μm，宽度为100cm，其中锂带的有效厚度为20μm。
本发明将实施例2制备的超薄锂带对SiOC极片进行预锂，与NCA进行组装电池。测试结果为：首次循环效率为98％。
随机选取中部一段50cm的锂带，纵向每隔1cm左右取一个点测量厚度，测量锂带两边和中间的厚度，共150个点；纵向测量两边和中间的厚度，每隔1cm测量一个点，一共测量30个点。
表3本发明实施例2提供的锂带纵向上不同点的有效厚度测试结果
Figure PCTCN2020116658-appb-000005
Figure PCTCN2020116658-appb-000006
Figure PCTCN2020116658-appb-000007
表4本发明实施例2提供的锂带纵向上不同点的有效厚度测试结果
Figure PCTCN2020116658-appb-000008
Figure PCTCN2020116658-appb-000009
由以上实施例可知，本发明提供了一种短流程制备大宽幅超薄金属锂箔的异步加热延压装置，包括牵引基材放卷单元，用来放卷牵引基材；锂带放卷单元，用来放卷锂带；异步加热压延单元，所述异步加热压延单元中包括第一延压辊、第二延压辊和加热箱；所述加热箱用来加热第一延压辊；所述第一延压辊对牵引基材进行加热；所述第一延压辊和第二延压辊轴线平行，对向设置，使牵引基材和锂带复合为复合带；收卷单元，用来收卷复合带。该装置通过设置加热箱和异步的第一延压辊和第二延压辊，能够制得厚度均一的大宽幅超薄金属锂箔；该锂箔应用在电池中具有较高的首效。实验结果表明：锂箔的宽度为1～600mm；所述锂箔的厚度为1～20μm；电池的首效高达98％；锂带横向上150个点作为测试点，有效厚度的相对误差为0～3％；纵向上30个点作为测试点，有效厚度的相对误差为0～2％。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (9)

  1. 一种短流程制备大宽幅超薄金属锂箔的异步加热延压装置，包括牵引基材放卷单元，用来放卷牵引基材；
    锂带放卷单元，用来放卷锂带；
    锂带预整形单元；
    异步加热压延单元，所述异步加热压延单元中包括第一延压辊、第二延压辊和加热箱；所述加热箱用来加热第一延压辊；所述第一延压辊对牵引基材进行加热；所述第一延压辊和第二延压辊轴线平行，对向设置，使牵引基材和锂带复合为复合带；
    收卷单元，用来收卷复合带。
  2. 根据权利要求1所述的异步加热延压装置，其特征在于，第二延压辊的表面包覆陶瓷层或聚合物层；所述陶瓷层包括氧化铝、氧化锆、氧化铬和复合物陶瓷涂层中的一种或多种；所述聚合物层包括聚硅氧烷、长链烷烃和石蜡中的一种或多种。
  3. 根据权利要求1所述的异步加热延压装置，其特征在于，所述锂带放卷单元中包括依次设置的锂带放卷辊、第一辅助导辊、第一张力检测辊和测速辊；
    所述牵引基材放卷单元中包括依次设置的基材放卷辊、第二辅助导辊、第一纠偏传感器、第三辅助导辊和第四辅助导辊；
    所述锂带预整形单元中包括依次设置的第二纠偏传感器和对向设置的整形辊；
    所述收卷单元中包括依次设置的第二张力检测辊、第三纠偏传感器和复合带收卷辊。
  4. 根据权利要求1所述的异步加热延压装置，其特征在于，所述牵引基材选自不锈钢箔，铜箔，钢箔或铁箔。
  5. 一种采用权利要求1～4任一项所述异步加热延压装置制备大宽幅超薄锂箔的方法，包括以下步骤：
    锂带经放卷和预整形后与放卷的牵引基材在第一延压辊和第二延压辊之 间的辊缝中异步加热压延处理，收卷，得到复合带；
    所述异步加热压延处理的温度为50～250℃；所述第二延压辊和第一延压辊的转速比为1:1.1～8。
  6. 根据权利要求5所述的方法，其特征在于，锂带放卷的速度为0.1～3m/min；牵引基材放卷的速度为0.1～20m/min。
  7. 根据权利要求5所述的方法，其特征在于，所述锂带放卷时的张力为5～100N；牵引基材和锂带放卷时的纠偏精度均为±0.2mm。
  8. 一种大宽幅超薄锂箔，由权利要求5～7任一项所述方法制得；
    所述锂箔的宽度为1～600mm；所述锂箔的厚度为1～20μm。
  9. 一种电池，包括权利要求8所述的大宽幅超薄锂箔。
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