CN111740178A - Method for improving electrical performance of lithium-rich manganese-based lithium ion battery - Google Patents

Method for improving electrical performance of lithium-rich manganese-based lithium ion battery Download PDF

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Publication number
CN111740178A
CN111740178A CN202010461362.6A CN202010461362A CN111740178A CN 111740178 A CN111740178 A CN 111740178A CN 202010461362 A CN202010461362 A CN 202010461362A CN 111740178 A CN111740178 A CN 111740178A
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charging
discharging
lithium
rich manganese
ion battery
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CN202010461362.6A
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姚晓辉
马洪运
易阳
周江
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Tianjin Juyuan New Energy Technology Co ltd
Tianjin Lishen Battery JSCL
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Tianjin Lishen Battery JSCL
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/448—End of discharge regulating measures
    • 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)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a method for improving the electrical property of a lithium-rich manganese-based lithium ion battery. The invention comprises the following steps: 1) under high voltage, applying certain pressure to the lithium ion battery, performing pre-charge and discharge for at least 3 times, wherein the charge cut-off voltage is lower than 4.6V; under the condition of applying a certain pressure P1, firstly charging to V0 by a small current I0, then charging to V1 by the current I, and discharging to V2 to finish primary pre-charging and discharging; then charging to V3 with current I, discharging to V2; completing the second pre-charge and discharge; finally, the current I is used for charging to V4 and discharging to V2, thus completing the pre-charging and discharging process. And step 2) applying a certain pressure P2 to the battery after the step 1), charging and discharging for not less than 1 time within a voltage range of V2-V5, and then keeping the pressure applied to use under the condition of different multiplying powers. The method is simple and feasible in process level, and can be beneficial to the industrial application of the lithium-rich manganese-based lithium ion battery.

Description

Method for improving electrical performance of lithium-rich manganese-based lithium ion battery
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a technical method capable of improving the electrical performance of a lithium-rich manganese-based lithium ion battery.
Background
Based on market demand considerations, battery energy density needs to be further increased. From the current technology, the high specific energy battery core adopts a high nickel anode material, and the ultimate specific energy which can be achieved by the high specific energy battery core is about 300Wh/kg, so the requirement of the industry on a new generation of high capacity anode material is particularly urgent. Among known cathode materials, the lithium-rich manganese-based cathode material has a specific discharge capacity of more than 250mAh/g, and the level of 400mAh/g has been reached in the prior research (Yuxuan Zuo, et al advanced materials,2018,1707255). Meanwhile, the material has low content of precious metal, and compared with the common lithium cobaltate and nickel cobalt manganese ternary system anode material, the material has low cost and good safety. Therefore, the lithium-rich manganese-based cathode material is regarded as the technical key of the next generation lithium ion power battery to break through 400 Wh/kg.
Although the lithium-rich manganese base can realize high capacity, if the industrialization of the power battery is realized, a series of technical difficulties still exist, such as 1) the problem of high-voltage gas production of materials, because of Li in the lithium-rich manganese base2MnO3Under high voltage (more than 4.5V), crystal lattice oxygen is gradually precipitated to provide higher capacity (Enyuan Hu, et al. Nature Energy,2018,3,690), but the precipitation of the crystal lattice oxygen causes serious gassing and swelling when the material is charged to high voltage (more than or equal to 4.6V) for the first time; 2) the first cycle irreversible capacity loss is large (Shuoqing Zhao, et al. Angewandte Chemie International Edtion,2020, DOI: 10.1002/anie.202000262); 3) the ionic conductivity and the electronic conductivity of the material are low, and the impedance is high; 4) technical difficulties of material recycling, etc.
In view of the above problems, current material development work mainly develops around material modification technologies, including bulk doping and interface cladding of materials. Bulk phase doping and surface coating modification (Jingsong Yang, et al. advanced energy Materials,2020, DOI: 10.1002/aenm.201904264; Wei Zhang, et al. advanced Materials,2020, DOI:10.1002/adma.202000496) of the material, most of the technologies are in scientific research and exploration stages at present, and the material technology cost is high. Besides the improvement of the material, if the technical problems are further solved simply and effectively in the process level, the industrial application of the lithium-rich manganese-based material is forcefully promoted.
Disclosure of Invention
The invention aims to provide a technical method which is simple and feasible in process level, can effectively improve the first reversible capacity under the high voltage of a lithium-rich manganese base, and simultaneously obviously improves the rate capability and the cycling stability of the lithium-rich manganese base lithium ion battery.
The steps adopted by the invention for realizing the aim are as follows:
1) under high voltage, applying certain pressure to the lithium ion battery, performing pre-charge and discharge for at least 3 times, wherein the charge cut-off voltage is lower than 4.6V; under the condition of applying a certain pressure P1, firstly charging to V0 by a small current I0, then charging to V1 by the current I, and discharging to V2 to finish primary pre-charging and discharging; then charging to V3 with current I, discharging to V2; completing the second pre-charge and discharge; finally, the current I is used for charging to V4 and discharging to V2, thus completing the pre-charging and discharging process. And step 2) applying a certain pressure P2 to the battery after the step 1), charging and discharging for not less than 1 time within a voltage range of V2-V5, and then keeping the pressure applied to use under the condition of different multiplying powers.
In the invention, the pre-charge and discharge system aims at activating the anode material in advance under lower voltage, on one hand, the film can be sequentially formed on the surface of the anode material to play a role of stabilizing the surface, and on the other hand, the Li can be slowly released2MnO3The large amount of crystal lattice oxygen precipitation polymerization of the components causes large amount of gas generation.
The clamp is utilized to apply pressure to the lithium ion battery, so that the pole pieces are attached to each other in the charging and discharging processes. During the charging and discharging process, if gas is separated out to cause the expansion of a battery core, the contact of a pole piece is poor, the ohmic impedance of the battery is obviously increased, and meanwhile, the deposition of byproducts formed by the uneven lithium intercalation of the positive pole and the negative pole occurs, so that the rapid attenuation of the circulation capacity is caused. The pressure of the clamp can effectively avoid a series of linkage influences caused by gas generation, and effectively improve the capacity, the circulation, the rate capability and the like of the material.
Preferably, the applied pressure P1 in the step (1) is 0.3-0.6MPa, and the proper pressure can improve the lithium intercalation uniformity in the positive electrode and the negative electrode.
Preferably, in step (1), the pressure P1 is 0.3-0.6MPa, I0 is 0.01C-0.05C, V0 is 3.6-4.0V, I is 0.1C-0.3C, V1 is 4.25-4.35V, V2 is 2-2.5V, V3 is 4.35-4.45V, and V4 is 4.45-4.6V. Due to direct charging to high voltage, lattice oxygen is violently precipitated and then polymerized to generate oxygen, so that the pole piece expands, reversible capacity is reduced, and interface films can be slowly formed on the surface of the material by stepwise low-potential pre-charging, so that the surface stability of the material is improved.
Preferably, in the step (2), the pressure P2 of the battery for completing the step 1) is 0.004-0.1MPa, the V2 is 2-2.5V, and the V5 is 4.6-4.7V, so that the battery can limit the significant change of ohmic impedance caused during the use process of the lithium ion battery.
The method provided by the invention is mainly applied to improving the electrical property of the lithium-rich manganese-based battery, can effectively inhibit gas production of the lithium-rich manganese-based battery, and overcomes the problems of cycle decay, low multiplying power and the like. Meanwhile, the technical method is simple and feasible in the process aspect, and can be beneficial to the industrial application of the lithium-rich manganese-based lithium ion battery.
Drawings
Fig. 1a is a capacity-voltage curve of a capacity calibration test (example 1) after a lithium-rich manganese-based soft package battery is subjected to three times of pre-charge and discharge systems respectively;
FIG. 1b is a capacity-voltage curve of the direct high-voltage charge-discharge regime (example 1');
FIG. 2a is a cycle life test curve using the jigs (example 2), respectively;
FIG. 2b is a cycle life test curve for charging and discharging without using a jig (example 2').
Detailed Description
The essential features and advantages of the invention will be further explained below with reference to examples, but the invention is not limited to the examples listed.
Example 1 Using a lithium-rich manganese-based Material Li1.2Ni0.13Co0.13Mn0.54O2And matching the graphite negative electrode to perform the procedures of pole piece preparation, pole group assembly and the like, and finishing the manufacture of the soft package laminated battery.
The battery was subjected to three times of pre-charge and discharge at a pressure of P1 and 1 time of charge and discharge at a pressure of P2.
In this embodiment, P1 is preferably 0.4MPa, and is first charged to 3.9V at a low current of 0.02C, then charged to 4.25V at a current of 0.1C, and discharged to 2.0V, thereby completing the first pre-charge and discharge; then charging to 4.35V at a current of 0.1C, and discharging to 2.0V; completing the second pre-charge and discharge; finally, charging to 4.5V by using the current of 0.1C, discharging to 2.0V, and finishing the third pre-charging and discharging process; p2 is preferably 0.1MPa, voltage interval is preferably 2V-4.6V, and charge-discharge current is preferably 0.2C.
Meanwhile, the assembled battery was implemented in comparative example 1', and was first charged to 3.9V at a small current of 0.02C and then directly charged to 4.6V at a current of 0.1C and discharged to 2.0V at a pressure of 0.4 MPa.
The result data show that the gram capacity discharged in the third pre-discharge of the battery in the embodiment 1 after pre-charging and discharging can reach 255mAh/g (see fig. 1a), the reversible gram capacity can reach 268mAh/g after 2-4.6V charging and discharging in the step 2), and no gas generation bulge behavior occurs; in contrast, the reversible gram capacity of the battery without three pre-charging and discharging processes in comparative example 1' is only 200mAh/g (see FIG. 1b), and the battery generates gas generation bulge behavior, which cannot meet the next electrical performance requirement.
Example 2 Using a lithium-rich manganese-based Material Li1.2Ni0.13Co0.13Mn0.54O2And matching the graphite negative electrode to perform the procedures of pole piece preparation, pole group assembly and the like, and finishing the manufacture of the soft package laminated battery. The battery was subjected to three times of pre-charge and discharge at a pressure of P1 and 1 time of charge and discharge at a pressure of P2, and then subjected to a cycle performance test.
In this embodiment, P1 is preferably 0.4MPa, and is first charged to 3.9V at a low current of 0.02C, then charged to 4.35V at a current of 0.1C, and discharged to 2.0V, thereby completing the first pre-charge and discharge; then charging to 4.45V at a current of 0.1C, and discharging to 2.0V; completing the second pre-charge and discharge; finally, charging to 4.55V by using the current of 0.1C, discharging to 2.0V, and finishing the third pre-charging and discharging process; in the high-voltage charging and discharging step, P2 is preferably 0.1Mpa, the voltage interval is preferably 2V-4.6V, the current is preferably 0.33C, and then the cyclic test under the same pressure of the same standard is carried out.
Meanwhile, the assembled battery is implemented in comparative example 2', and three times of pre-charging and discharging of the same system are carried out under the pressure of 0.4 MPa. Then, a cycle test of 2-4.6V and 0.33C was carried out without applying pressure.
The result data show that after the batteries in the example 2 and the comparative example 2' are subjected to pre-charging, the discharging gram capacity can reach 261mAh/g during the third pre-discharging; in the subsequent 2-4.6V charging and discharging steps in the embodiment 2, the reversible gram capacity can reach 260mAh/g, the circulation capacity retention rate is more than or equal to 500 circles @ 80% (see figure 2a), and in the comparative example 2', the subsequent circulation capacity is rapidly reduced, and the capacity retention rate is only 100 circles @ 80% (see figure 2 b).
The above-described technical disclosure of the performance enhancement of the lithium-rich manganese-based battery with reference to the embodiments is illustrative and not restrictive, and thus, variations and modifications thereof without departing from the general inventive concept are intended to be included within the scope of the present invention.

Claims (4)

1. A method for improving the electrical property of a lithium-rich manganese-based lithium ion battery is characterized in that the following steps are carried out on the assembled lithium-rich manganese-based lithium ion battery:
1) at high voltage, performing pre-charge discharge for at least 3 times within the range of applied pressure P1:0.3-0.6MPa, wherein the charge cut-off voltage is lower than 4.6V; step 2) applying a pressure P2 to the battery completing step 1): charging and discharging at 0.004-0.1MPa at 4.6V for at least 1 time, and maintaining the pressure under different multiplying power conditions.
2. The method of claim 1, wherein the positive active material of the lithium-rich manganese-based lithium ion battery comprises a lithium-rich manganese-based oxide, the negative active material comprises at least one of silicon and graphite, and the lithium-rich manganese-based lithium ion battery is of a soft package type.
3. The method of claim 1, wherein step (1) comprises first charging the lithium-rich manganese-based lithium ion battery with a low current I0: 0.01C-0.05C to V0: 3.6-4.0V, then with current I: 0.1C-0.3C to V1: 4.25-4.35V, discharge to V2: 2-2.5V, completing the first pre-charge and discharge; then charged to V3 with current I: 4.35-4.45V, and then discharging to V2; completing the second pre-charge and discharge; finally, charge to V4 with current I: 4.45-4.6V, and discharging to V2 to complete the third pre-charge-discharge process.
4. The method for improving the electrical property of the lithium-rich manganese-based lithium ion battery according to claim 1, wherein the step (2) comprises charging and discharging not less than 1 time in a voltage interval with a lower limit cut-off voltage of 2-2.5V and an upper limit cut-off voltage of 4.6-4.7V, and applying a pressure in a range of 0.004-0.1MPa in subsequent charging and discharging use.
CN202010461362.6A 2020-05-27 2020-05-27 Method for improving electrical performance of lithium-rich manganese-based lithium ion battery Pending CN111740178A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106684457A (en) * 2017-01-18 2017-05-17 合肥国轩高科动力能源有限公司 Formation method for high-voltage lithium ion flexibly packaged battery
CN107959071A (en) * 2017-11-15 2018-04-24 国联汽车动力电池研究院有限责任公司 A kind of lithium ion battery and its chemical synthesizing method
CN108258347A (en) * 2017-12-28 2018-07-06 国联汽车动力电池研究院有限责任公司 A kind of chemical synthesizing method of silicium cathode soft bag lithium ionic cell
CN109713387A (en) * 2018-12-27 2019-05-03 肇庆遨优动力电池有限公司 A method of improving lithium-rich manganese-based lithium ion battery cyclical stability

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106684457A (en) * 2017-01-18 2017-05-17 合肥国轩高科动力能源有限公司 Formation method for high-voltage lithium ion flexibly packaged battery
CN107959071A (en) * 2017-11-15 2018-04-24 国联汽车动力电池研究院有限责任公司 A kind of lithium ion battery and its chemical synthesizing method
CN108258347A (en) * 2017-12-28 2018-07-06 国联汽车动力电池研究院有限责任公司 A kind of chemical synthesizing method of silicium cathode soft bag lithium ionic cell
CN109713387A (en) * 2018-12-27 2019-05-03 肇庆遨优动力电池有限公司 A method of improving lithium-rich manganese-based lithium ion battery cyclical stability

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