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Charging method and charging device of lithium metal battery

A lithium metal battery and charging method technology, applied in battery circuit devices, secondary battery charging/discharging, circuit devices, etc., can solve problems such as short life, potential safety hazards, and reduced battery life

Active Publication Date: 2022-07-08
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

If the initial constant voltage is used for charging, the larger voltage will cause positive electrode materials such as lithium cobaltate (3.9V, layered structure), nickel-cobalt-manganese ternary (3.8V, layered structure) and lithium iron phosphate (3.4V , polyanionic structure) and other structural collapse or even pulverization (Masashi Okubo,SeongjaeKo, DebasmitaDwibedi . Designing positive electrodes with high energydensity for lithium-ion batteries[J]. Journal of Materials Chemistry A, 2021,9:7407-7421. ), leading to rapid decay of battery capacity and a significant reduction in battery life
Second, in the charging process of lithium-ion batteries, if the initial constant voltage charging is used, the initial charging current will be huge. Although a large current means that the charging speed will be accelerated, the polarization effect generated by the initial huge current will make the potential of the negative electrode side continue to decrease. , and finally dropped below 0V, resulting in lithium precipitation on the surface of the negative electrode, affecting the service life, and even causing safety hazards (Trini, M; Jørgensen, Hauch P , et al. Journal of The Electrochemical Society - Research outputs - Research -Journal articles - DTU Orbit (09 / 03 / 2019).)
[0013] In view of the essential difference in the energy storage mechanism between lithium-ion batteries and lithium-metal batteries explained in the background technology, the charging method designed based on the core problems of lithium-ion batteries cannot be directly transplanted into lithium-metal batteries to take effect, even constant voltage and The effect of constant current, the two most basic charging building blocks, on lithium metal deposition is also unknown
The inventors found that lithium metal batteries operated with the standard charging protocol CC-CV are prone to short-circuit lithium dendrites under fast charging conditions, and have a short lifespan. Therefore, it is necessary to systematically explore the two most basic charging methods of constant voltage and constant current. The impact of structural units on lithium metal deposition, and the invention of new fast charging methods specifically suitable for lithium metal batteries to suppress the generation of lithium dendrites, which is very important for the development of high-energy fast charging battery systems

Method used

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  • Charging method and charging device of lithium metal battery
  • Charging method and charging device of lithium metal battery
  • Charging method and charging device of lithium metal battery

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0086] Assemble the same battery as in Comparative Example 1: Assemble the negative metal lithium and the positive copper sheet into a lithium copper battery, and the electrolyte is 1M LiTFSI / DOL-DME / 2% LiNO 3 .

[0087] The actual working voltage of the lithium-copper battery is calculated and detected by the charging device, which is 0V, and the rated power is 1mAh·cm -2 .

[0088] Example 1 is the whole process of constant voltage charging, and the deposition process adopts constant voltage, and the conditions are as follows: the deposition voltage is 0.25V, and the deposition power is 1mAh·cm -2 , the average deposition time is less than 5min; the stripping current is 1mA·cm -2 . The deposition power and the deposition time are the charging power and the charging time.

[0089] Constant voltage deposition is constant voltage charging, corresponding to CV 1 -CC-CV 2 CV in method 1 , CV 1 The value is the actual working voltage of the battery + 0.25V, that is, CV 1 ...

Embodiment 2

[0096] Assemble the same battery as in Comparative Example 2: 45 μm thick thin metal lithium sheet is used as the negative electrode and the positive lithium titanate electrode is assembled into a lithium metal battery (lithium-lithium titanate battery), and the electrolyte is 1M LiTFSI / DOL-DME / 2 % LiNO 3 .

[0097] The actual working voltage of the lithium-lithium titanate battery is calculated and detected by the charging device, which is 1.55V (vs Li + / Li)), the rated power is the rated power described in Comparative Example 2.

[0098] using CV 1 -CC-CV 2 Protocol charging, cycle test, the conditions are as follows: constant voltage charging, charging voltage CV 1 The value is the actual working voltage of the battery +0.35V, which is 1.9 V (vs Li + / Li).

[0099] Example 2 is the whole process of constant voltage charging. The charging cut-off condition is that the charging current density is less than the minimum value, that is, less than 0.03C, and then the singl...

Embodiment 3

[0107] Assemble the same battery as in Comparative Example 3: a 45 μm thin metal lithium sheet is used as the negative electrode and the positive sulfur electrode sheet to assemble a lithium metal-based battery, and the electrolyte is 1M LiTFSI / DOL-DME / 2% LiNO 3 .

[0108] The actual working voltage of the lithium-sulfur battery is calculated and detected by the charging device, which is 2.1V (vs Li + / Li)), the rated power is the rated power described in Comparative Example 3.

[0109] Charging with CV 1 -CC-CV 2 method, the cycle test is carried out under the following conditions: constant voltage charging, charging voltage CV 1 The value is the actual working voltage of the battery +0.45V, which is 2.55 V (vs Li + / Li).

[0110] Example 3 is the whole process of constant voltage charging. The charging cut-off condition is that the charging current density is less than the minimum value, that is, less than 0.03C, and then the single-turn charging stops and discharges; t...

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Abstract

The invention relates to a charging method and a charging device of a lithium metal battery, and the charging method is a first constant voltage charging and subsequent constant current-constant voltage coupling charging method, namely a CV1-CC-CV2 charging method. According to the charging method provided by the invention, constant-voltage charging is adopted in the initial stage, and the charging method is essentially different from initial constant-current charging in a standard charging method. According to the charging method, the initial constant voltage stage is introduced before a standard charging protocol, the internal electric field of the battery can be enhanced, lithium ions in electrolyte are promoted to migrate to a negative electrode, rapid consumption of interface lithium ions during rapid charging is slowed down, and compared with a traditional charging method, the method can enable lithium deposition to be compact and smooth, and plays roles in inhibiting growth of lithium dendrites and improving the charging efficiency. The service life is prolonged; and the quick charging safety is improved.

Description

technical field [0001] The invention relates to the field of batteries, in particular to a charging method and a charging device for a lithium metal battery. Background technique [0002] Lithium-ion batteries are widely used in smart phones, notebook computers, electric vehicles and other fields, but with the development of society, existing commercial lithium-ion batteries have been unable to meet people's growing demand for ultra-long battery life and fast charging electronic products. demand. Lithium metal has 3860 mAh g -1 Ultra-high theoretical specific capacity (graphite is 372mAh g -1 ) and the lowest redox potential (-3.04 V relative to standard hydrogen potential), which can greatly improve the battery energy density. Active lithium metal has the characteristics of fast kinetic reaction, so it also has the application potential of fast charging. Based on this, lithium metal batteries using metal-containing lithium foils as negative electrodes are receiving incr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/44H01M10/48H01M10/052H02J7/00
CPCH01M10/44H01M10/48H01M10/052H02J7/00712H02J7/0048Y02E60/10
Inventor 陆盈盈王鑫阳
Owner ZHEJIANG UNIV
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