CN113097452A - Pre-lithiation device - Google Patents

Pre-lithiation device Download PDF

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Publication number
CN113097452A
CN113097452A CN202110355305.4A CN202110355305A CN113097452A CN 113097452 A CN113097452 A CN 113097452A CN 202110355305 A CN202110355305 A CN 202110355305A CN 113097452 A CN113097452 A CN 113097452A
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China
Prior art keywords
conveying
conveying section
lithiation
section
prelithiation
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Chinese (zh)
Inventor
邱昭政
李文龙
赵育松
梁世硕
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Kunshan Bao Innovative Energy Technology Co Ltd
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Kunshan Bao Innovative Energy Technology Co Ltd
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Priority to CN202110355305.4A priority Critical patent/CN113097452A/en
Publication of CN113097452A publication Critical patent/CN113097452A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a prelithiation device. The pre-lithiation device comprises a pre-lithiation tank, a cleaning tank, a drying chamber and a conveying device, wherein the conveying device comprises a first conveying section, a second conveying section, a third conveying section and a fourth conveying section which are sequentially connected; the first conveying section is arranged in the pre-lithiation tank, the second conveying section is arranged between the pre-lithiation tank and the cleaning tank, the third conveying section is arranged in the cleaning tank, the fourth conveying section is arranged close to the drying chamber, and the part to be pre-lithiated sequentially passes through the pre-lithiation tank, the cleaning tank and the drying chamber under the conveying of the first conveying section, the second conveying section, the third conveying section and the fourth conveying section; the pre-lithiation tank is internally provided with a first stirring device and used for containing a pre-lithiation reagent, and the cleaning tank is internally provided with a second stirring device and used for containing a cleaning agent. The pre-lithiation device can enable the silicon-oxygen negative plate with high surface density and high compaction density to complete the pre-lithiation process within an acceptable time, and can enable the negative plate to have small volume expansion in the pre-lithiation process.

Description

Pre-lithiation device
Technical Field
The invention relates to a pre-lithiation device, and belongs to the field of lithium ion batteries.
Background
In order to improve the mileage problem of the electric vehicle, the research and development of the power battery are gradually developing towards a long endurance direction. In the prior art, the silicon-based material and the graphite particles are compounded as the negative active material, so that the energy density of the battery can be improved, the battery can be ensured to have good rate capability, and the electric automobile is endowed with good long-term endurance. Since pure silicon carbon material has a severe volume effect during charging and discharging, which may cause a rapid reduction in the cycle life of the battery, the industry is more inclined to use silicon oxygen material as the negative active material of the power battery. Since the silicon monoxide material contains a large amount of O element, a large amount of Li source is consumed by materials forming an SEI film and lithium silicate/lithium oxide during the formation process, which results in low first efficiency of the battery.
In the prior art, the first effect of a silicon-oxygen negative electrode sheet is improved by performing pre-lithiation on the silicon-oxygen negative electrode sheet, so that the first effect of a lithium ion battery is improved. Prelithiation refers to the introduction of exogenous lithium into the battery system in a suitable manner and morphology to ameliorate the first coulombic efficiency reduction due to the depletion of available lithium by the silicon oxygen cathode. Currently, the prelithiation is mainly divided into positive prelithiation and negative prelithiation, and the negative prelithiation is divided into direct addition of exogenous lithium, active additive prelithiation, electrochemical prelithiation and chemical prelithiation according to a prelithiation mode. The chemical prelithiation is simple to operate and has low requirements on a drying environment, so that researchers pay attention to the prelithiation technical research in recent years.
However, when the pre-lithiated target is a negative electrode sheet with high areal density, high compaction density and thickness, it takes a very long time for the electrode sheet to be completely infiltrated by the chemical pre-lithiation reagent during the pre-lithiation, and the reaction time of the pre-lithiation after infiltration is longer. Moreover, soaking the negative electrode plate in a liquid chemical pre-lithiation reagent for a long time can cause the negative electrode plate to expand greatly in volume, so that the thickness of the finished battery is increased, and the battery is deformed and difficult to group.
Disclosure of Invention
The invention provides a prelithiation device, which has short prelithiation time and small volume expansion of a negative plate when the prelithiation device prelithiates the negative plate with high surface density, high compaction density and thicker thickness.
The invention provides a pre-lithiation device which comprises a pre-lithiation tank, a cleaning tank, a drying chamber and a conveying device, wherein the conveying device comprises a first conveying section, a second conveying section, a third conveying section and a fourth conveying section which are sequentially connected;
the first conveying section is arranged in the pre-lithiation tank, the second conveying section is arranged between the pre-lithiation tank and the cleaning tank, the third conveying section is arranged in the cleaning tank, the fourth conveying section is arranged close to the drying chamber, and a part to be pre-lithiated sequentially passes through the pre-lithiation tank, the cleaning tank and the drying chamber under the conveying of the first conveying section, the second conveying section, the third conveying section and the fourth conveying section;
the pre-lithiation tank is internally provided with a first stirring device and used for containing a pre-lithiation reagent, and the cleaning tank is internally provided with a second stirring device and used for containing a cleaning agent.
The prelithiation apparatus as described above, wherein the prelithiation reagent comprises a Li-polycyclic aromatic hydrocarbon methyl derivative;
the polycyclic aromatic hydrocarbon methyl derivative is selected from at least one of methyl substituent of biphenyl, methyl substituent of terphenyl, methyl substituent of diphenylmethane, methyl substituent of fluorene and methyl substituent of anthracene.
The prelithiation device as described above, wherein the first stirring device has a rotation speed of 5 to 200 r/min; and/or the presence of a gas in the gas,
the rotating speed of the second stirring device is 5-200 r/min.
The prelithiation device is characterized in that the prelithiation tank is further provided with a first heating device, and the temperature of the first heating device is 25-80 ℃; and/or the presence of a gas in the gas,
the cleaning tank is further provided with a second heating device, and the temperature of the second heating device is 25-80 ℃.
The prelithiation device as described above, wherein the first conveying section comprises N first conveying rollers, the first conveying rollers are respectively located at the inlet, the bottom and the outlet of the prelithiation tank, and N is greater than or equal to 3.
The prelithiation device as described above, wherein the third conveying section includes F third conveying rollers, the second conveying rollers are respectively located at the inlet, the bottom and the outlet of the washing tank, and F is greater than or equal to 3.
The prelithiation apparatus as described above, wherein the fourth conveying section comprises M fourth conveying rollers, the fourth conveying rollers are respectively located at the inlet and the outlet of the drying chamber, and M ≧ 2.
The prelithiation apparatus as described above, wherein the prelithiation apparatus further comprises a rolling device, the transport apparatus further comprising a fifth transport section proximate the rolling device, the fifth transport section being connected to the first transport section;
and the part to be pre-lithiated sequentially passes through the rolling device, the pre-lithiation tank, the washing tank and the drying chamber under the conveying of the fifth conveying section, the first conveying section, the second conveying section, the third conveying section and the fourth conveying section.
The prelithiation device as described above, wherein the fifth conveying section includes L fifth conveying rollers, the fifth conveying rollers are located at the inlet of the rolling device, the to-be-prelithiation member passes through the rolling device under the conveying of the fifth conveying rollers, and L is greater than or equal to 1.
The prelithiation device as described above, further comprising a winding device, wherein the winding device comprises a first winding section, a second winding section and a third winding section;
the first rolling section is arranged at the starting end of the fourth conveying section, the second rolling section is arranged between the fifth conveying section and the first conveying section, and the third rolling section is arranged at the terminal of the fourth conveying section.
The pre-lithiation device comprises a pre-lithiation tank, a cleaning tank, a drying chamber and a conveying device, wherein the conveying device comprises a first conveying section, a second conveying section, a third conveying section and a fourth conveying section which are sequentially connected; the first conveying section is arranged in the pre-lithiation tank, the second conveying section is arranged between the pre-lithiation tank and the cleaning tank, the third conveying section is arranged in the cleaning tank, the fourth conveying section is arranged close to the drying chamber, and a part to be pre-lithiated sequentially passes through the pre-lithiation tank, the cleaning tank and the drying chamber under the conveying of the first conveying section, the second conveying section, the third conveying section and the fourth conveying section; the pre-lithiation tank is internally provided with a first stirring device and used for containing a pre-lithiation reagent, and the cleaning tank is internally provided with a second stirring device and used for containing a cleaning agent. The arrangement of the first stirring device and the second stirring device can enable the silicon-oxygen negative plate with high surface density and high compaction density to complete the pre-lithiation process under the condition of shortening the pre-lithiation time, and can inhibit the volume expansion of the negative plate in the pre-lithiation process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the related art, the drawings used in the description of the embodiments of the present invention or the related art are briefly introduced below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic structural view of a prelithiation apparatus according to a first embodiment of the present invention;
fig. 2 is a schematic structural diagram of a prelithiation apparatus according to a second embodiment of the present invention;
fig. 3 is a schematic structural view of a prelithiation apparatus according to a third embodiment of the present invention;
fig. 4 is a schematic structural diagram of a prelithiation apparatus according to a fourth embodiment of the present invention.
Description of reference numerals:
1: a pre-lithiation tank;
2: a cleaning tank;
3: a drying chamber;
4: a first transfer section;
5: a second transfer section;
6: a third transfer section;
7: a fourth transfer section;
8: a first stirring device;
9: a second stirring device;
10: a first transfer roller;
11: a third transfer roller;
12: a fourth transfer roller;
13: a rolling device;
14: a fifth transfer section;
15: a fifth transfer roller;
16: a first winding section;
17: a second winding section;
18: a third winding section;
19: a sixth transfer roller;
20: a second transfer roller.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fig. 1 is a schematic structural diagram of a prelithiation device according to a first embodiment of the present invention. As shown in fig. 1, the present invention provides a pre-lithiation apparatus, comprising a pre-lithiation tank 1, a washing tank 2, a drying chamber 3 and a conveying device, wherein the conveying device comprises a first conveying section 4, a second conveying section 5, a third conveying section 6 and a fourth conveying section 7 which are connected in sequence;
the first conveying section 4 is arranged in the pre-lithiation tank 1, the second conveying section 5 is arranged between the pre-lithiation tank 1 and the cleaning tank 2, the third conveying section 6 is arranged in the cleaning tank 2, the fourth conveying section 7 is arranged close to the drying chamber 3, and the part to be pre-lithiated sequentially passes through the pre-lithiation tank 1, the cleaning tank 2 and the drying chamber 3 under the conveying of the first conveying section 4, the second conveying section 5, the third conveying section 6 and the fourth conveying section 7;
the pre-lithiation tank 1 is internally provided with a first stirring device 8 for accommodating a pre-lithiation reagent, and the cleaning tank 2 is internally provided with a second stirring device 9 for accommodating a cleaning agent.
The pre-lithiation tank 1 is used for containing a pre-lithiation reagent, the pre-lithiation reagent is used for pre-lithiating a part to be pre-lithiated, the cleaning tank 2 is used for containing a cleaning reagent, and the cleaning reagent is used for cleaning the pre-lithiation reagent remained on the part to be pre-lithiated after pre-lithiation. In the invention, the part to be pre-lithiated is conveyed to a pre-lithiation tank 1 through a first conveying section 4 for pre-lithiation, then conveyed to a washing tank 2 under the conveying of a second conveying section 5 and a third conveying section 6 to wash away pre-lithiation reagent remained on the part to be pre-lithiated, and finally conveyed to a drying chamber through a fourth conveying section 7 for drying, so that the pre-lithiation part is obtained. The invention does not limit the specific structure of the conveying device of the part to be pre-lithiated, and the conveying device can be a conveying belt or a conveying roller.
The invention is not limited to the specific structure of the part to be prelithiated, and in a specific embodiment, the part to be prelithiated is a silicon-oxygen negative electrode sheet. According to the invention, the first stirring device 8 is arranged in the pre-lithiation tank 1 to help the pre-lithiation process to be accelerated, the second stirring device 9 is arranged in the cleaning tank 2 to help the pre-lithiation reagent remained on the pre-lithiation part after pre-lithiation to be removed, and the arrangement of the first stirring device 8 and the second stirring device 9 can enable the pre-lithiation part with high surface density and high compaction density to complete the pre-lithiation process in as short a time as possible, so that the pre-lithiation efficiency is improved, and the volume expansion of the pre-lithiation part in the pre-lithiation process can be inhibited by shortening the pre-lithiation time.
In some embodiments of the invention, the prelithiation reagent comprises a Li-polycyclic aromatic hydrocarbon methyl derivative;
the polycyclic aromatic hydrocarbon methyl derivative is at least one selected from methyl substituent of biphenyl, methyl substituent of terphenyl, methyl substituent of diphenylmethane, methyl substituent of fluorene and methyl substituent of anthracene.
In a particular embodiment, the polycyclic aromatic hydrocarbon methyl derivative is selected from the group consisting of 3,3 ' -dimethylbiphenyl, 4,4 ' -dimethylbiphenyl (4,4 ' -DMBP), 2-methylbiphenyl, 3 ', 4,4 ' -tetramethylbiphenyl, 9-dimethyl-9H-fluorene.
The relationship between the oxidation-reduction potential of the chemical prelithiation reagent and the oxidation-reduction potential of the silicon-based anode material can greatly influence the prelithiation effect. The oxidation-reduction potential of the silicon-based negative electrode material is usually 0.2V, when the oxidation-reduction potential of the pre-lithiation reagent is higher than that of the silicon-based negative electrode material, the pre-lithiation reagent can only form an SEI film on the surface of the silicon-based negative electrode material, but can not embed lithium in a bulk phase of the silicon-based negative electrode material, and can not form the SEI film in the bulk phase. The polycyclic aromatic hydrocarbon methyl derivative selected in the present invention has an oxidation-reduction potential of less than 0.2V, and illustratively, the oxidation-reduction potential of 0.131V when 2-methylbiphenyl is obtained by substituting the ortho position of biphenyl with 1 methyl group, the oxidation-reduction potential of 0.294V when 3,3 '-dimethylbiphenyl is obtained by substituting the meta position of biphenyl with 2 methyl groups, the oxidation-reduction potential of 0.186V when 4, 4' -dimethylbiphenyl is obtained by substituting the para position of biphenyl with 2 methyl groups, and the oxidation-reduction potential of 0.129V when 3,3 ', 4, 4' -tetramethylbiphenyl is obtained by substituting the meta position and the para position of biphenyl with 4 methyl groups. When the polycyclic aromatic hydrocarbon methyl derivative is used as a prelithiation reagent, the silicon-based part to be prelithiated can be subjected to more effective prelithiation treatment.
In a specific embodiment, the Li-polycyclic aromatic hydrocarbon methyl derivative can be prepared by adding metallic lithium to a mixture of the polycyclic aromatic hydrocarbon methyl derivative and an organic solvent. The organic solvent may be ethers or furans as the solvent. The lithium metal may be at least one of lithium powder, lithium foil, lithium sheet or lithium block. In this prelithiation solution, the Li-polycyclic aromatic hydrocarbon methyl derivative is the active species that plays a role in prelithiation. In the prelithiation solution, the prelithiation reagent has a concentration of 0.2 to 3.0 mol/L.
The cleaning agent of the present invention may be an organic solvent, and in some embodiments, the organic solvent may be at least one of carbonates, ethers, or furans having a low boiling point. In a specific embodiment, the organic solvent may be at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dimethyl ether, diethyl ether, or tetrahydrofuran. According to the invention, the organic solvent is used for extracting the pre-lithiation reagent, so that the pre-lithiation reagent on the surface and in pores of the pre-lithiation part to be pre-lithiated can be more thoroughly removed, and the influence of the residual pre-lithiation reagent on the performance of the battery can be reduced.
When the rotating speed of the first stirring device 8 is too low, the too low stirring rotating speed in the pre-lithiation tank 1 limits the acceleration degree of the pre-lithiation process, and when the rotating speed of the first stirring device 8 is too high, the too high stirring rotating speed in the pre-lithiation tank 1 causes too large energy consumption. When the rotating speed of the second stirring device 9 is too low, the too low stirring rotating speed in the cleaning tank 2 is limited in acceleration degree of the cleaning process, and when the rotating speed of the second stirring device 9 is too high, the too high stirring rotating speed in the cleaning tank 2 is too high, so that the energy consumption is too large.
The invention limits the rotating speed of the first stirring device 8 and the second stirring device 9, and can more fully accelerate the pre-lithiation process and the cleaning process on the premise of not generating excessive energy consumption. In some embodiments of the present invention, the rotation speed of the first stirring device 8 is 5 to 200 r/min; and/or the presence of a gas in the gas,
the rotating speed of the second stirring device 9 is 5-200 r/min.
Further, the rotating speed of the first stirring device 8 is 10-150 r/min; the rotating speed of the second stirring device 9 is 10-150 r/min.
When the temperature of first heating device is too low, the speed of prelithiation is slower, and when the temperature of first heating device was too high, prelithiation reagent can volatilize to the energy consumption increases, when the temperature of second heating device was too low, the washing speed was slower, and when the temperature of second heating device was too high, the organic solvent in washing tank 2 can volatilize, and the energy consumption increases.
The invention limits the temperature of the first heating device and the temperature of the second heating device, and can accelerate the pre-lithiation process and the cleaning process under the conditions of not generating excessive energy consumption and not causing volatilization of the pre-lithiation reagent and the organic reagent in the cleaning tank 2. In some embodiments of the invention, the prelithiation tank 1 is further provided with a first heating device, and the temperature of the first heating device is 25-80 ℃; and/or the presence of a gas in the gas,
the cleaning tank 2 is also provided with a second heating device, and the temperature of the second heating device is 25-80 ℃.
Furthermore, the temperature of the first heating device is 30-80 ℃, and the temperature of the second heating device is 30-80 DEG C
In a specific embodiment, when the rotating speed of the first stirring device 8 is 15-120 r/min, the temperature of the first heating device is 30-75 ℃, the rotating speed of the second stirring device 9 is 15-120 r/min, and the temperature of the second heating device is 30-75 ℃, the pre-lithiation effect and the cleaning effect are better.
Fig. 2 is a schematic structural diagram of a prelithiation device according to a second embodiment of the present invention. As shown in FIG. 2, in some embodiments of the present invention, the first conveying section 4 comprises N first conveying rollers 10, the first conveying rollers 10 are respectively located at the inlet, the bottom and the outlet of the pre-lithiation bath 1, and N ≧ 3.
In the invention, the part to be pre-lithiated enters the pre-lithiation tank 1 under the conveying of the first conveying roller 10 to be pre-lithiated to obtain a pre-lithiation part, and is output from the pre-lithiation tank.
In some embodiments, the second conveying section 5 comprises G second conveying rollers 20, the second conveying rollers 20 are respectively close to the outlet of the pre-lithiation tank 1 and the inlet of the cleaning tank 2, and G is larger than or equal to 2.
As shown in FIG. 2, in some embodiments of the present invention, the third transfer section 6 includes F third transfer rolls 11, the third transfer rolls 11 are respectively located at the inlet, bottom and outlet of the wash tank 2, and F ≧ 3.
In the invention, the pre-lithiated part to be pre-lithiated, which is output from the pre-lithiation tank 1, enters the cleaning tank 2 under the conveying of the third conveying roller 11 to clean the pre-lithiation reagent remained on the pre-lithiated part to be pre-lithiated, and the cleaned pre-lithiated part to be pre-lithiated is output from the cleaning tank 2.
As shown in FIG. 2, in some embodiments of the present invention, the fourth conveying section 7 includes M fourth conveying rollers 12, the fourth conveying rollers 12 are respectively located at the inlet and the outlet of the drying chamber 3, and M ≧ 2.
The pre-lithiated member to be pre-lithiated after washing in the present invention is dried by passing through the drying chamber 3 under the conveyance of the fourth conveying roller 12.
Fig. 3 is a schematic structural diagram of a prelithiation apparatus according to a third embodiment of the present invention. As shown in fig. 3, in some embodiments of the present invention, the prelithiation apparatus further comprises a rolling device 13, the conveyor further comprises a fifth conveyor section 14 adjacent to the rolling device 13, the fifth conveyor section 14 being connected to the first conveyor section 4;
the parts to be pre-lithiated pass through a rolling device 13, a pre-lithiation tank 1, a cleaning tank 2 and a drying chamber 3 in sequence under the conveying of a fifth conveying section 14, a first conveying section 4, a second conveying section 5, a third conveying section 6 and a fourth conveying section 7.
In the invention, the rolling device 13 is arranged before the first conveying section 4, so that the pre-lithiation component entering the pre-lithiation tank 1 can be prevented from wrinkling, and the pre-lithiation component entering the pre-lithiation tank 1 can be fully pre-lithiated. The invention does not limit the specific structure of the rolling device 13, and all structures which can roll the pre-lithiation part belong to the protection scope of the invention.
As shown in FIG. 3, in some embodiments of the present invention, the fifth conveying section 14 includes L fifth conveying rollers 15, the fifth conveying rollers 15 are located at the inlet of the rolling device 13, and the pre-lithiation member passes through the rolling device 13 under the conveying of the fifth conveying rollers 15, L ≧ 1.
The part to be pre-lithiated enters a rolling device 13 for rolling under the conveying of a fifth conveying roller 15 to obtain the rolled part to be pre-lithiated. The present invention does not limit the specific number of the fifth transfer rollers 15, and it is within the scope of the present invention as long as the number L of the fifth transfer rollers 15 is equal to or greater than 1.
The transfer device of the invention may also comprise a sixth transfer roller 19 arranged at the outlet of the rolling device 13.
Fig. 4 is a schematic structural diagram of a prelithiation apparatus according to a fourth embodiment of the present invention. As shown in fig. 4, in some embodiments of the present invention, a winding device is further included, and the winding device includes a first winding section 16, a second winding section 17, and a third winding section 18;
the first winding section 16 is disposed at the start end of the fifth conveying section 14, the second winding section 17 is disposed between the fifth conveying section 14 and the first conveying section 4, and the third winding section 18 is disposed at the end of the fourth conveying section 7.
In the invention, the first winding section 16 is used for winding the to-be-prelithiated part, the second winding section 17 can prevent the to-be-prelithiated part entering the prelithiation groove 1 from having wrinkles when the to-be-prelithiated part output by the rolling device 13 is too much, and the third winding section 18 is used for winding the to-be-prelithiated part which is completed with prelithiation.
In a specific embodiment, the pre-lithiation component enters the fifth conveying section 14 through the first rolling section 16, enters the rolling device 13 through the fifth conveying section 14, enters the second rolling section 17 after being rolled by the rolling device 13, enters the first conveying section 4 through the second rolling section 17, is conveyed through the first conveying section 4, is pre-lithiated in the pre-lithiation tank 1, is conveyed to the third conveying section 6 through the second conveying section 5, is conveyed through the third conveying section 6, is cleaned from the pre-lithiation component remaining on the pre-lithiation component in the cleaning tank 2, is conveyed to the drying chamber 3 through the fourth conveying section 7 to be dried to obtain the pre-lithiation component, and enters the third rolling section 18 to be rolled.
The invention is further illustrated by the following specific examples in which all parts, percentages, and ratios recited in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and used as such without further treatment, and the equipment used in the examples is commercially available.
Example 1
The structure of the pre-lithiation device in this embodiment is shown in fig. 4, and includes a pre-lithiation tank, a cleaning tank, a drying chamber, and a conveying device, where the conveying device includes a first conveying section, a second conveying section, a third conveying section, and a fourth conveying section, which are connected in sequence;
the first conveying section is arranged in the pre-lithiation tank, the second conveying section is arranged between the pre-lithiation tank and the cleaning tank, the third conveying section is arranged in the cleaning tank, the fourth conveying section is arranged close to the drying chamber, and the part to be pre-lithiated sequentially passes through the pre-lithiation tank, the cleaning tank and the drying chamber under the conveying of the first conveying section, the second conveying section, the third conveying section and the fourth conveying section;
a first stirring device is arranged in the pre-lithiation tank and used for accommodating a pre-lithiation reagent, and a second stirring device is arranged in the cleaning tank;
the pre-lithiation device further comprises a rolling device, the conveying device further comprises a fifth conveying section close to the rolling device, and the fifth conveying section is connected with the first conveying section;
the part to be pre-lithiated sequentially passes through the rolling device, the pre-lithiation tank, the cleaning tank and the drying chamber under the conveying of the fifth conveying section, the first conveying section, the second conveying section, the third conveying section and the fourth conveying section.
Example 2
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1) preparation of negative plate
Mixing silicon monoxide and graphite according to the mass ratio of 1:10 to prepare a negative electrode active material with the specific capacity of 464mAh/g, mixing the negative electrode active material, conductive carbon black (SP) serving as a conductive agent and a binder (CMC-SBR,1/1wt) according to the mass ratio of 80:12:8, adding a proper amount of deionized water to obtain negative electrode active slurry, coating the negative electrode active slurry on two functional surfaces of a Cu foil, and drying to obtain a negative electrode sheet. The surface density of the negative plate is 10mg/cm2The compacted density is 1.5g/cm3。
2) Preparation of prelithiation reagent
Adding lithium foil into a dimethyl ether (DME) solution dissolved with Li-4,4 '-dimethylbiphenyl (Li-4, 4' -DMBP) in a glove box, and stirring to obtain a Li-4,4 '-DMBP compound solution with the concentration of 1.0mol/L, wherein the Li-4, 4' -DMBP compound solution is used as a prelithiation reagent;
3) prelithiation
Pre-lithiation is carried out by adopting the pre-lithiation device in the embodiment 1, the pre-lithiation reagent in the step 2) is placed in a pre-lithiation tank, the negative plate in the step 1) is conveyed by a first conveying section after being rolled by a rolling device, pre-lithiation is carried out in the pre-lithiation tank, the negative plate is conveyed to a third conveying section by a second conveying section, the pre-lithiation reagent remained on the negative plate is cleaned in a cleaning tank by the third conveying section, the pre-lithiation reagent remained on the negative plate is conveyed by a fourth conveying section, and drying is carried out in a drying chamber to obtain a pre-lithiated negative plate;
wherein the rotating speed of the first stirring device is 20r/min, the temperature of the first heating device is 35 ℃, and the prelithiation time is 15 min; the cleaning agent in the cleaning tank is EC/DEC (1:1v/v) solvent, the rotating speed of the second stirring device is 20r/min, the second heating temperature is 50 ℃, and the cleaning time is 10 min.
4) Preparation of Positive plate
Mixing Li (Ni)0.5Co0.2Mn0.3)O2Mixing the positive electrode active material, SP and PVDF binder at a mass ratio of 84:8:8, adding N-methylpyrrolidone (NMP) to obtain positive electrode active slurry, and coating the positive electrode active slurry on the functional surface of the carbon-coated Al foil to obtain a positive electrode sheet.
5) Preparation of lithium ion battery
Assembling the pre-lithiated negative plate obtained in the step 3), the positive plate obtained in the step 4) and the diaphragm into a battery, and injecting electrolyte to prepare the full battery.
Example 3
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 2, except that in the step 1), the silicon monoxide and the graphite are mixed according to the mass ratio of 1:5 to prepare the negative electrode active material with the specific capacity of 550 mAh/g.
Example 4
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 2, except that in the step 1), the silicon monoxide and the graphite are mixed according to the mass ratio of 1:1 to prepare the negative electrode active material with the specific capacity of 930 mAh/g.
Example 5
The preparation procedure of the lithium ion battery of this example is substantially the same as that of example 2, except that the areal density of the negative electrode sheet in step 1) is 2mg/cm2。
Example 6
The procedure for preparing the lithium ion battery of this example is substantially the same as that of example 2, except that the areal density of the negative electrode sheet in step 1) is 16mg/cm2。
Example 7
The procedure for preparing the lithium ion battery of this example was substantially the same as in example 2, except that the compacted density of the negative electrode sheet in step 1) was 1.0mg/cm3。
Example 8
The procedure for preparing the lithium ion battery of this example was substantially the same as in example 2, except that the compacted density of the negative electrode sheet in step 1) was 1.4mg/cm3。
Example 9
The procedure for preparing the lithium ion battery of this example was substantially the same as in example 2, except that the compacted density of the negative electrode sheet in step 1) was 1.7mg/cm3。
Example 10
The procedure for preparing the lithium ion battery of this example was substantially the same as in example 2, except that the concentration of the prelithiation agent in step 2) was 0.5 mol/L.
Example 11
The procedure for preparing the lithium ion battery of this example was substantially the same as in example 2, except that the concentration of the prelithiation agent in step 2) was 3.0 mol/L.
Example 12
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 2, except that the rotating speed of the first stirring device in the step 3) is 5r/min, the temperature of the first heating device is 50 ℃, and the prelithiation time is 10 min.
Example 13
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 2, except that the rotating speed of the first stirring device in the step 3) is 200r/min, the temperature of the first heating device is 25 ℃, and the prelithiation time is 30 min.
Example 14
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 2, except that the rotating speed of the first stirring device in the step 3) is 100r/min, the temperature of the first heating device is 80 ℃, and the prelithiation time is 2 min.
Example 15
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 2, except that the rotating speed of the first stirring device in the step 3) is 50r/min, the temperature of the first heating device is 45 ℃, and the prelithiation time is 10 min.
Example 16
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 2, except that the rotation speed of the second stirring device in the step 3) is 5r/min, the temperature of the second heating device is 80 ℃, and the cleaning time is 2 min.
Example 17
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 2, except that the rotation speed of the second stirring device in the step 3) is 100r/min, the temperature of the second heating device is 50 ℃, and the cleaning time is 10 min.
Example 18
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 2, except that the rotation speed of the second stirring device in the step 3) is 30r/min, the temperature of the second heating device is 25 ℃, and the cleaning time is 30 min.
Example 19
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 2, except that the rotation speed of the second stirring device in the step 3) is 20r/min, the temperature of the second heating device is 45 ℃, and the cleaning time is 15 min.
Example 20
The procedure for preparing the lithium ion battery of this example was substantially the same as in example 2, except that the prelithiation agent in step 2) was a 1.0mol/L Li-biphenyl (Li-BP) complex.
Example 21
The procedure for preparing the lithium ion battery of this example was substantially the same as in example 2, except that the prelithiation agent in step 2) was a 1.0mol/L Li-3,3 '-dimethylbiphenyl (Li-3, 3' -DMBP) complex.
Example 22
The procedure for preparing the lithium ion battery of this example was substantially the same as in example 2, except that the prelithiation agent in step 2) was a 1.0mol/L Li-2-methylbiphenyl (Li-2-MBP) complex.
Example 23
The procedure for preparing the lithium ion battery of this example was substantially the same as in example 2, except that the prelithiation reagent in step 2) was a 1.0mol/L Li-3,3 ', 4, 4' -tetramethylbiphenyl (Li-3,3 ', 4, 4' -TMBP) complex.
Example 24
The procedure for preparing the lithium ion battery of this example was substantially the same as in example 2, except that the prelithiation reagent in step 2) was 1.0mol/L of Li-9.9-dimethyl-9H-fluorene complex.
Example 25
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 7, and the only difference is that the rotating speed of the first stirring device in the step 3) is 20r/min, the temperature of the first heating device is 30 ℃, and the prelithiation time is 10 min;
example 26
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 8, and the only difference is that the rotating speed of the first stirring device in the step 3) is 45r/min, the temperature of the first heating device is 35 ℃, and the prelithiation time is 20 min;
example 27
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 9, and the only difference is that the rotating speed of the first stirring device in the step 3) is 90r/min, the temperature of the first heating device is 60 ℃, and the prelithiation time is 30 min;
example 28
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 10, and the only difference is that the rotating speed of the first stirring device in the step 3) is 35r/min, the temperature of the first heating device is 40 ℃, and the prelithiation time is 25 min;
example 29
The preparation steps of the lithium ion battery of the embodiment are basically the same as those of the embodiment 11, and the only difference is that the rotating speed of the first stirring device in the step 3) is 50r/min, the temperature of the first heating device is 40 ℃, and the prelithiation time is 10 min;
comparative example 1
The preparation steps of the lithium ion battery of the comparative example are basically the same as those of the example 2, and the only difference is that the negative electrode sheet obtained in the step 1), the positive electrode sheet obtained in the step 4) and the diaphragm are assembled into a battery in the step 5), and electrolyte is injected to prepare the full battery.
Comparative example 2
The procedure for preparing the lithium ion battery of this comparative example was substantially the same as in example 2, except that in step 3), the first stirring device and the second stirring device were not provided.
Performance testing
1) First effect
a. Specific discharge capacity: the manufactured negative plate is cut into a circular plate with the diameter of 14mm, the circular plate is assembled into a 2032 type button cell, the button cell is discharged to the cutoff voltage of 0.005V by the current of 0.2C, the discharge capacity is recorded, and the first discharge specific capacity is calculated according to the load capacity of the negative active material.
b. Charging specific capacity: and C, charging the button battery which is completely discharged in the step a to 2.0V by 0.2C current, recording the charging capacity, and calculating the first charging specific capacity according to the loading capacity of the active material of the negative electrode material.
c. First efficiency of button cell: specific capacity of button cell for first charge/first discharge.
2) Energy density
Energy density of the whole battery: preparing an anode, a cathode and a diaphragm into an 8Ah battery core in a lamination mode, injecting electrolyte (the liquid retention coefficient is 2.7g/Ah), forming at a rate of 0.2C under the condition that a voltage window is 2.7-4.25V, wherein the discharge rate is 0.5C, and calculating the energy density of the whole battery according to the 3 rd discharge capacity, the discharge platform and the weight of the battery.
3) Capacity retention after 200 weeks of cycling
Capacity retention rate at 200 weeks: the discharge capacity at the 201 th cycle was recorded and the capacity retention rate was calculated by performing charge-discharge cycles at room temperature (23 ℃) for 200 weeks on a 0.5C/0.5C cycle system.
TABLE 1
Figure BDA0003003476410000161
Figure BDA0003003476410000171
As can be seen from table 1, the prelithiation device of the present invention can prelithiate a negative electrode sheet with high areal density and high compaction density, and the lithium ion battery prepared from the prelithiated negative electrode sheet has high first efficiency, high energy density and high capacity retention rate.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. A pre-lithiation device is characterized by comprising a pre-lithiation tank, a cleaning tank, a drying chamber and a conveying device, wherein the conveying device comprises a first conveying section, a second conveying section, a third conveying section and a fourth conveying section which are sequentially connected;
the first conveying section is arranged in the pre-lithiation tank, the second conveying section is arranged between the pre-lithiation tank and the cleaning tank, the third conveying section is arranged in the cleaning tank, the fourth conveying section is arranged close to the drying chamber, and a part to be pre-lithiated sequentially passes through the pre-lithiation tank, the cleaning tank and the drying chamber under the conveying of the first conveying section, the second conveying section, the third conveying section and the fourth conveying section;
the pre-lithiation tank is internally provided with a first stirring device and used for containing a pre-lithiation reagent, and the cleaning tank is internally provided with a second stirring device and used for containing a cleaning agent.
2. The prelithiation device of claim 1, wherein the prelithiation reagent comprises a Li-polycyclic aromatic hydrocarbon methyl derivative;
the polycyclic aromatic hydrocarbon methyl derivative is selected from at least one of methyl substituent of biphenyl, methyl substituent of terphenyl, methyl substituent of diphenylmethane, methyl substituent of fluorene and methyl substituent of anthracene.
3. The prelithiation device of claim 1 or 2, wherein the first stirring device has a rotational speed of 5 to 200 r/min; and/or the presence of a gas in the gas,
the rotating speed of the second stirring device is 5-200 r/min.
4. The prelithiation device according to any one of claims 1 to 3, wherein the prelithiation cell is further provided with a first heating device, the first heating device having a temperature of 25 to 80 ℃; and/or the presence of a gas in the gas,
the cleaning tank is further provided with a second heating device, and the temperature of the second heating device is 25-80 ℃.
5. The prelithiation apparatus of any one of claims 1 to 4, wherein the first transport section comprises N first transport rollers, N ≧ 3, at the inlet, bottom, and outlet, respectively, of the prelithiation cell.
6. The prelithiation apparatus of claim 5, wherein the third conveyor section comprises F third conveyor rollers, the third conveyor rollers being located at the inlet, bottom, and outlet of the wash tank, respectively, F ≧ 3.
7. The prelithiation apparatus of claim 6, wherein the fourth conveyor section comprises M fourth conveyor rollers, wherein M is greater than or equal to 2, and wherein the fourth conveyor rollers are located at the inlet and outlet of the drying chamber, respectively.
8. The prelithiation device of any one of claims 1 to 7, wherein the prelithiation device further comprises a roller press device, the transport device further comprising a fifth transport segment proximate the roller press device, the fifth transport segment being connected to the first transport segment;
and the part to be pre-lithiated sequentially passes through the rolling device, the pre-lithiation tank, the washing tank and the drying chamber under the conveying of the fifth conveying section, the first conveying section, the second conveying section, the third conveying section and the fourth conveying section.
9. The prelithiation device according to claim 8, wherein the fifth conveying section comprises L fifth conveying rollers, the fifth conveying rollers are located at the inlet of the rolling device, the member to be prelithiated passes through the rolling device under the conveying of the fifth conveying rollers, and L is greater than or equal to 1.
10. The prelithiation device of claim 9, further comprising a take-up device comprising a first take-up section, a second take-up section, and a third take-up section;
the first rolling section is arranged at the starting end of the fifth conveying section, the second rolling section is arranged between the fifth conveying section and the first conveying section, and the third rolling section is arranged at the terminal of the fourth conveying section.
CN202110355305.4A 2021-04-01 2021-04-01 Pre-lithiation device Pending CN113097452A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
WO2020235841A1 (en) * 2019-05-17 2020-11-26 주식회사 엘지화학 Negative electrode manufacturing device and negative electrode manufacturing method
CN112563458A (en) * 2020-12-11 2021-03-26 上海纳米技术及应用国家工程研究中心有限公司 Device for chemical prelithiation of aromatic hydrocarbons

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Publication number Priority date Publication date Assignee Title
WO2020235841A1 (en) * 2019-05-17 2020-11-26 주식회사 엘지화학 Negative electrode manufacturing device and negative electrode manufacturing method
CN112563458A (en) * 2020-12-11 2021-03-26 上海纳米技术及应用国家工程研究中心有限公司 Device for chemical prelithiation of aromatic hydrocarbons

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