CN111668568B - Formation process of lithium ion battery - Google Patents

Formation process of lithium ion battery Download PDF

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CN111668568B
CN111668568B CN202010592156.9A CN202010592156A CN111668568B CN 111668568 B CN111668568 B CN 111668568B CN 202010592156 A CN202010592156 A CN 202010592156A CN 111668568 B CN111668568 B CN 111668568B
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current
charging
voltage
battery
constant
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CN111668568A (en
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赵瑞荣
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GUANGZHU YANGHE ELECTRONIC TECHNOLOGY Co.,Ltd.
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Guangzhu Yanghe Electronic Technology Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • H01M10/446Initial charging measures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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

Abstract

The invention provides a lithium ion battery formation process, which comprises the steps of preheating an electrolyte, injecting liquid, pre-activating a battery by low-current pre-charging, then combining multi-stage pulse charging, constant-current discharging, multi-stage pulse charging, high-current charging and constant-voltage charging processes with gradually increasing currents, controlling the SEI generation speed by controlling parameters of different stages, facilitating the formation of a compact SEI film, eliminating concentration polarization in the battery and effectively improving the cycle performance and the storage performance of the battery.

Description

Formation process of lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a formation process of a lithium ion battery.
Background
As a novel clean energy, the lithium ion battery has the advantages of high working voltage, high energy density, light weight and the like, and is widely applied to the fields of 3C consumption, new energy automobiles, unmanned aerial vehicles and the like. Due to the increase of the universality of the use, more strict requirements are required, and besides the improvement of battery materials and manufacturing processes, the battery manufacturing method is further optimized. Formation is an important link in the battery manufacturing process, and aims to form a layer of solid electrolyte interface film (SEI) on an electrode material in the battery in the first charging and discharging process of the battery, and the performance of the battery in the aspects of high capacity, low cycle life, high-temperature storage and the like is directly influenced by the quality of the formation process.
The traditional formation process adopts low-current charging to form an SEI film, but the SEI film is easy to be unstable, the active material capacity exertion efficiency is low, and the rate capability is poor.
The invention aims to provide a lithium ion battery formation process to solve the problems in the conventional lithium ion battery formation process.
Disclosure of Invention
The invention provides a lithium ion battery formation process, which comprises the following steps:
(1) heating the electrolyte to 40-80 ℃, and injecting liquid into the flexible package lithium ion battery;
(2) placing the battery in a formation cabinet at 40-80 deg.C, and charging to 20-50% SOC at constant current of 0.01-0.03 deg.C;
(3) three-stage pulse charging is carried out, wherein the current of the first stage is 0.05-0.2C, the pulse time is 90-120s, and the interval is 5-10 s; the second-stage current is 0.3-0.5C, the pulse time is 50-80s, and the interval is 5-10 s; the current of the third section is 0.8-1C, the interval is 5-10s, the voltage of the battery reaches the charge cut-off voltage, and constant-voltage charging is carried out under the charge cut-off voltage until the charge current is lower than 0.01C;
(4) discharging at constant current of 0.1-0.5 deg.C to first voltage U1, and regulating current to 0.05-0.08 deg.C to discharge at constant current to cut-off voltage;
(5) two-stage pulse charging: the first-stage current is 0.3-0.5C, the pulse time is 50-80s, and the interval is 5-10 s; the second-stage current is 0.8-1C, the pulse time is 10-20s, and the interval is 5-10 s;
(6) charging to a charge cut-off voltage at a constant current of 0.5-1C; charging at constant voltage with a charge cut-off voltage until the current is lower than 0.01C;
(7) and (4) standing the charged battery at high temperature, exhausting air and sealing.
The preparation process of the battery comprises the following steps: the positive electrode adopts lithium cobaltate, the negative electrode adopts graphite, the diaphragm adopts a commercial PP diaphragm, the electrolyte adopts EC/EMC/DEC type electrolyte, and vinylene carbonate VC and fluoroethylene carbonate FEC are used as additives.
Has the advantages that:
according to the invention, the electrolyte is preheated and injected, and a high-temperature state is kept in the formation process, so that the viscosity of the electrolyte is reduced, the infiltration of the electrolyte is facilitated, the lithium ion transmission rate is increased, the generation of an SEI film is accelerated, and the formation time is shortened; the low-current pre-charging is used for pre-activating the battery, so that the electrochemical reaction is fully performed, the processes of pulse charging, constant-current discharging, large-current constant-current charging and constant-voltage charging with multi-section current increasing are combined, different parameters are adjusted at different stages to control the film forming speed, a compact SEI film is favorably formed, concentration polarization in the battery is eliminated, and the cycle performance of the battery is effectively improved.
Detailed Description
Example 1
A lithium ion battery formation method comprises the following steps:
(1) heating the electrolyte to 40 ℃, and injecting liquid into the flexible package lithium ion battery;
(2) placing the battery in a formation cabinet, adjusting the temperature of the formation cabinet to 40 ℃, and charging the battery to 30% SOC at a constant current of 0.01 ℃;
(3) three-stage pulse charging, wherein the first-stage current is 0.05C, the pulse time is 90s, and the interval is 5 s; the second section current is 0.3C, the pulse time is 50s, and the interval is 5 s; the current of the third section is 0.8C, the interval is 5s, the battery voltage reaches the charging cut-off voltage, and the constant voltage charging is carried out under the charging cut-off voltage until the charging current is lower than 0.01C;
(4) discharging to 2.4V at a constant current of 0.1C, and then adjusting the current to 0.01C for constant current discharge to a discharge cut-off voltage;
(5) two-stage pulse charging: the first section current is 0.3C, the pulse time is 50s, and the interval is 5 s; the second section current is 1C, the pulse time is 10s, and the interval is 5 s;
(6) charging to a charge cut-off voltage at a constant current of 0.5C; charging at constant voltage with a charge cut-off voltage until the current is lower than 0.01C;
(7) and (4) standing the charged battery at high temperature, exhausting air and sealing.
Example 2:
a lithium ion battery formation method comprises the following steps:
(1) heating the electrolyte to 50 ℃, and injecting liquid into the flexible package lithium ion battery;
(2) placing the battery in a formation cabinet, adjusting the temperature of the formation cabinet to 50 ℃, and charging to 50% SOC at a constant current of 0.01 ℃;
(3) three-stage pulse charging, wherein the first-stage current is 0.1C, the pulse time is 90s, and the interval is 5 s; the second section current is 0.4C, the pulse time is 50s, and the interval is 5 s; the current of the third section is 1C, the interval is 5s, until the voltage of the battery reaches the charging cut-off voltage, the constant voltage charging is carried out under the charging cut-off voltage until the charging current is lower than 0.01C;
(4) discharging to 2.2V at a constant current of 0.1C, and then adjusting the current to 0.01C for constant current discharge to a discharge cut-off voltage;
(5) two-stage pulse charging: the first section current is 0.4C, the pulse time is 60s, and the interval is 5 s; the second section current is 1C, the pulse time is 10s, and the interval is 5 s;
(6) charging to a charge cut-off voltage at a constant current of 0.8C; charging at constant voltage with a charge cut-off voltage until the current is lower than 0.01C;
(7) and (4) standing the charged battery at high temperature, exhausting air and sealing.
Comparative example 1:
(1) filling liquid into the flexible package lithium ion battery at room temperature;
(2) placing the battery in a room temperature formation cabinet, and charging the battery to 30% SOC at a constant current of 0.01C;
(3) charging to 60% SOC at 0.1C constant current, followed by charging at 0.2C constant current until the battery voltage reaches a charge cut-off voltage, and constant voltage charging at the charge cut-off voltage until the charge current is less than 0.01C;
(4) standing the charged battery at high temperature, exhausting air and sealing, and finishing formation;
the prepared single cells of examples 1-2 and comparative examples were tested for 500 weeks at 1C at 100% DOD for charge-discharge cycles, the cell was disassembled to observe the interfacial conditions, and the following table shows the cell performance comparison of examples 1-2 and comparative examples.
Capacity retention rate of 500 cycles Pole piece interface conditions
Example 1 93.1% No black spot
Example 2 94.1% No black spot
Comparative example 1 86.4% Has black spots
TABLE 1
Analysis of the experimental data of examples 1-2 and comparative examples shows that the formation of a dense SEI film by the formation method of examples 1-2 effectively prevents the formation of black spots on the electrode plate and effectively improves the cycle performance of the battery.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (1)

1. A lithium ion battery formation method comprises the following steps:
(1) heating the electrolyte to 40-60 ℃, and injecting liquid into the lithium ion battery;
(2) placing the battery in a formation cabinet, wherein the temperature of the formation cabinet is 40-60 ℃, and charging the battery to 20-50% SOC at a constant current of 0.01-0.03 ℃;
(3) three-stage pulse charging is carried out, wherein the current of the first stage is 0.05-0.2C, the pulse time is 90-120s, and the interval is 5-10 s; the second-stage current is 0.3-0.5C, the pulse time is 50-80s, and the interval is 5-10 s; the current of the third section is 0.8-1C, the interval is 5-10s, the voltage of the battery reaches the charge cut-off voltage, and constant-voltage charging is carried out under the charge cut-off voltage until the charge current is lower than 0.01C;
(4) discharging with constant current of 0.1-0.2C to first voltage of 2.1-2.5V, and regulating current to 0.01-0.03C to discharge with constant current to cut-off voltage;
(5) two-stage pulse charging: the first-stage current is 0.3-0.5C, the pulse time is 50-80s, and the interval is 5-10 s; the second-stage current is 0.8-1C, the pulse time is 10-20s, and the interval is 5-10 s;
(6) charging to a charge cut-off voltage at a constant current of 0.5-1C; charging at constant voltage with a charge cut-off voltage until the current is lower than 0.01C;
(7) and (4) standing the charged battery at high temperature, exhausting air and sealing, thus finishing formation.
CN202010592156.9A 2020-06-24 2020-06-24 Formation process of lithium ion battery Active CN111668568B (en)

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CN113471428A (en) * 2021-05-20 2021-10-01 福建海峡石墨烯产业技术研究院有限公司 Method for improving graphite or graphene negative electrode stability of potassium ion battery and potassium ion battery
CN114188596B (en) * 2021-11-23 2023-09-01 郑州比克电子有限责任公司 Pre-activation method of lithium ion battery

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101154746A (en) * 2006-09-28 2008-04-02 比亚迪股份有限公司 Formation method for lithium ion secondary battery
CN101179121A (en) * 2006-11-09 2008-05-14 比亚迪股份有限公司 Method for pouring non-water electrolysing solution into battery case during the process of power cell preparation
CN101777669A (en) * 2010-02-02 2010-07-14 江西联威新能源有限公司 Precharging formation method for lithium ion battery
CN103367813A (en) * 2013-07-23 2013-10-23 惠州市泰格威电池有限公司 Formation processing method of lithium manganate battery
CN106532160A (en) * 2016-12-29 2017-03-22 宁德新能源科技有限公司 Battery charging method and device
CN106532159A (en) * 2016-12-29 2017-03-22 宁德新能源科技有限公司 Battery charging method and device
CN109148991A (en) * 2018-10-09 2019-01-04 邓丽萍 A kind of chemical synthesizing method of long-life flexible-packed battery

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101154746A (en) * 2006-09-28 2008-04-02 比亚迪股份有限公司 Formation method for lithium ion secondary battery
CN101179121A (en) * 2006-11-09 2008-05-14 比亚迪股份有限公司 Method for pouring non-water electrolysing solution into battery case during the process of power cell preparation
CN101777669A (en) * 2010-02-02 2010-07-14 江西联威新能源有限公司 Precharging formation method for lithium ion battery
CN103367813A (en) * 2013-07-23 2013-10-23 惠州市泰格威电池有限公司 Formation processing method of lithium manganate battery
CN106532160A (en) * 2016-12-29 2017-03-22 宁德新能源科技有限公司 Battery charging method and device
CN106532159A (en) * 2016-12-29 2017-03-22 宁德新能源科技有限公司 Battery charging method and device
CN109148991A (en) * 2018-10-09 2019-01-04 邓丽萍 A kind of chemical synthesizing method of long-life flexible-packed battery

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