CN114335421A - Reference electrode of three-electrode battery, and vehicle - Google Patents
Reference electrode of three-electrode battery, and vehicle Download PDFInfo
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- CN114335421A CN114335421A CN202111649734.9A CN202111649734A CN114335421A CN 114335421 A CN114335421 A CN 114335421A CN 202111649734 A CN202111649734 A CN 202111649734A CN 114335421 A CN114335421 A CN 114335421A
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Abstract
The invention provides a reference electrode of a three-electrode battery, the three-electrode battery and a vehicle. A diaphragm is arranged between the reference electrode and the anode of the three-electrode battery, and a diaphragm is arranged between the reference electrode and the cathode of the three-electrode battery; the reference electrode comprises a copper-antimony composite material, and a lithium-containing compound is deposited on the surface of the reference electrode through an alloying reaction. Therefore, the lithium can be well fixed on the surface of the reference electrode, the lithium can be uniformly deposited on the surface of the reference electrode, the lithium is not easy to react with the electrolyte in the subsequent circulation process, the lithium deposited on the surface of the reference electrode is effectively prevented from being damaged, and the lithium-ion battery has good structural stability and potential stability.
Description
Technical Field
The invention relates to the field of batteries, in particular to a reference electrode of a three-electrode battery, the three-electrode battery and a vehicle.
Background
In the prior art, in order to eliminate errors of electrode potential caused by polarization current in a two-electrode system, a reference electrode for stabilizing a working electrode can be introduced on the basis of a conventional two-electrode system (a working motor and a counter electrode).
Generally, for a lithium ion battery, a three-electrode system can be constructed by depositing lithium on the surface of a copper wire as a reference electrode. However, on the one hand, the deposited lithium is liable to react with the electrolyte and cannot be kept in a stable state during cell cycling or storage, which in turn may cause the three-electrode system of the lithium ion battery to fail in a short period of time. On the other hand, as shown in the schematic diagram of the reference electrode lithium plating process shown in fig. 1, metal lithium is deposited on the surface of the copper wire to complete lithium plating, but in the cycle process of the lithium ion battery, the reference electrode can easily react with the electrolyte, but the lithium metal layer is damaged, and the three-electrode system fails.
Disclosure of Invention
The invention aims to provide a reference electrode of a three-electrode battery, the three-electrode battery and a vehicle, so that the stability of the three-electrode system lithium ion battery can be kept well in the circulating process.
In order to solve the above problems, embodiments of the present invention provide a reference electrode of a three-electrode battery, where a separator is disposed between the reference electrode and a positive electrode of the three-electrode battery, and a separator is disposed between the reference electrode and a negative electrode of the three-electrode battery; the reference electrode comprises a copper-antimony composite material, and a lithium-containing compound is deposited on the surface of the reference electrode through an alloying reaction.
Optionally, the copper-antimony composite material is prepared by at least one of chemical plating of an antimony layer on the surface of a copper substrate, chemical plating of an antimony layer on the surface of the copper substrate, and chemical vapor plating of an antimony layer on the surface of the copper substrate.
Optionally, the thickness of the antimony layer is 1-25 μm.
Optionally, the lithium-containing compound is LixSb(0<x≤3)。
Optionally, the lithium-containing compound is generated by charging between the positive electrode and the reference electrode of the three-electrode battery by using preset charging and discharging equipment, so that the reference electrode and the lithium metal are subjected to alloying reaction.
Alternatively, the lithium-containing compound is obtained by an alloying reaction of the formula:
optionally, the surface of the copper-antimony composite material is coated with an insulating layer.
Optionally, the potential of the reference electrode is 0.8V (vs Li/Li +).
Embodiments of the present invention also provide a three-electrode battery including the reference electrode according to embodiments of the present invention.
The embodiment of the invention also provides a vehicle which comprises the three-electrode battery.
Compared with the prior art, the invention has the following advantages:
according to the reference electrode of the three-electrode battery provided by the embodiment of the invention, a diaphragm is arranged between the reference electrode and the anode of the three-electrode battery, and a diaphragm is arranged between the reference electrode and the cathode of the three-electrode battery; the reference electrode comprises a copper-antimony composite material, and a lithium-containing compound is deposited on the surface of the reference electrode through an alloying reaction. Therefore, the lithium can be well fixed on the surface of the reference electrode, the lithium can be uniformly deposited on the surface of the reference electrode, the lithium is not easy to react with the electrolyte in the subsequent circulation process, the lithium deposited on the surface of the reference electrode is effectively prevented from being damaged, and the lithium-ion battery has good structural stability and potential stability.
Drawings
FIG. 1 is a schematic diagram of a prior art reference electrode lithium plating process;
fig. 2 is a schematic diagram of a reference electrode lithium plating process provided by an embodiment of the invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
The embodiment of the invention provides a reference electrode of a three-electrode battery, wherein a diaphragm is arranged between the reference electrode and a positive electrode of the three-electrode battery, and a diaphragm is arranged between the reference electrode and a negative electrode of the three-electrode battery; the reference electrode comprises a copper-antimony composite material, and a lithium-containing compound is deposited on the surface of the reference electrode through an alloying reaction.
Specifically, the reference electrode of the three-electrode battery provided in the embodiment of the present invention has a separator provided between the reference electrode and the positive electrode of the three-electrode battery, and a separator provided between the reference electrode and the negative electrode of the three-electrode battery. The diaphragm can effectively isolate the electrodes from each other, thereby avoiding the internal short circuit of the lithium ion battery of the three-electrode system and ensuring the safe operation of the lithium ion battery of the three-electrode system.
In the specific implementation, a material with good comprehensive properties such as good mechanical strength, thermal stability, high dielectric constant and the like can be used as the diaphragm, for example, a diaphragm made of a fluoropolymer such as polyvinylidene fluoride, a ceramic-coated diaphragm, a boron nitride-coated diaphragm and the like, which is not limited in the present invention.
In particular, in order that lithium may be stably deposited on the reference electrode, the reference electrode may include a copper antimony composite. During the lithium plating process, antimony in the copper-antimony composite material can perform an alloying reaction with lithium contained in the lithium ion battery to form a lithium-containing compound, so that lithium can be well fixed on the surface of the reference electrode. In this case, lithium is not simply attached to the surface of the reference electrode, but may form an alloy phase with antimony, so that lithium dendrite formation may be effectively prevented. In the subsequent circulation process, the lithium-containing chemical compound of the alloy phase is not easy to react with the electrolyte, so that the lithium deposited on the surface of the reference electrode is effectively prevented from being damaged, and the lithium-containing chemical compound has good structural stability and potential stability.
In one embodiment of the invention, the copper-antimony composite material is prepared by at least one of chemical plating of an antimony layer on the surface of a copper substrate, chemical plating of an antimony layer on the surface of the copper substrate and vapor plating of an antimony layer on the surface of the copper substrate.
Specifically, antimony layer may be added to the surface of the copper substrate by surface chemical, surface plating, or surface deposition, so that antimony capable of alloying with lithium is provided on the surface of the copper substrate. Therefore, in the subsequent alloying reaction process, lithium can react with antimony on the surface of the copper-antimony composite material to form an alloy on the surface of the copper base material, so that the lithium plating on the surface of the copper base material is realized.
As a specific example of the present invention, fig. 2 is a schematic diagram of a reference electrode lithium plating process according to an embodiment of the present invention. The reference electrode is additionally provided with an antimony layer on the surface of the copper substrate, antimony can generate an alloying reaction with lithium in the lithium plating process, and a lithium-containing compound is formed on the surface of the copper substrate. Thereby realizing stable adhesion of lithium to the surface of the copper substrate. In the subsequent battery cycle process, lithium and antimony form a lithium-containing compound through an alloying reaction, and the lithium cannot be easily separated from a lithium-containing chemical substance, so that the lithium can be stably fixed on the surface of the reference electrode all the time in the use process of the lithium ion battery, the reference electrode can keep good structural stability and potential stability, and the safety of the lithium ion battery is effectively improved.
In one embodiment of the present invention, the thickness of the antimony layer is 1 to 25 μm.
Specifically, the thickness of the antimony layer on the surface of the copper substrate may be 1 to 25 μm so that lithium ions can be deposited on the surface of the copper substrate. If the thickness of the antimony layer on the surface of the copper substrate is too thin, it may be difficult for the surface of the copper substrate to store sufficient lithium in the lithium-containing chemical formed on the surface of the copper substrate, which may result in a decrease in the performance of the reference electrode. Meanwhile, in the case that the antimony layer is too thin, the formed alloy layer may be too thin, thereby affecting the stability of the reference electrode. If the thickness of the antimony layer on the surface of the copper substrate is too thick, excessive lithium may be stored on the surface of the copper substrate, which may cause a change in current density of an alloy layer formed on the surface of the reference electrode, and may cause a failure in normal operation of a lithium ion battery of a three-electrode system. Under the condition that the thickness of the antimony layer on the surface of the copper substrate can be 1-25 mu m, the reference electrode has good stability, the current density is moderate, and the good operation of the lithium ion battery of a three-electrode system can be kept.
In one embodiment of the invention, the lithium-containing compound is LixSb(0<x≤3)。
Specifically, the lithium-containing chemical compound formed by the alloying reaction of antimony and lithium may be LixAnd (5) Sb. And x is more than 0 and less than or equal to 3. Thus, lithium can be efficiently deposited on the surface of the copper substrate through the antimony layer, and Li is formed due to antimony and lithiumxThe Sb alloy has good structural stability and potential stability, and can effectively improve the stability of the reference electrode. Meanwhile, one Sb layer can form an alloy with 1-3 Li, so that the Sb layer can efficiently store lithium on the surface of the copper substrate.
In one embodiment of the present invention, the lithium-containing compound is generated by an alloying reaction between a reference electrode and metallic lithium by charging between a positive electrode and the reference electrode of the three-electrode battery by using a preset charging and discharging device.
Specifically, there are many different ways to provide the reference electrode, for example, a way of directly implanting metallic lithium as the reference electrode, a way of directly assembling the reference electrode between the positive electrode and the negative electrode of the lithium ion battery, etc. can be adopted. However, in these methods, the metal lithium is directly assembled into the lithium ion battery as the reference electrode, on one hand, the metal lithium still has the possibility of reacting with the electrolyte, and on the other hand, the reference electrode has a large size, locally affects lithium ion migration, shields the electric field between the positive electrode and the negative electrode, and needs to be operated in an inert atmosphere, which makes the technical scheme difficult to implement. Therefore, the reference electrode and the lithium metal can be generated through an alloying reaction by charging between the positive electrode and the reference electrode of the three-electrode battery by adopting preset charging and discharging equipment. The method for processing the reference electrode can effectively control the size of the reference electrode, has small influence on the performance of the battery and can be operated in an air environment. The alloying reaction of the reference electrode can be completed with higher precision, so that the metallic lithium is better deposited on the surface of the reference electrode.
Based on electrochemical alloying reaction, lithium can be diffused into the antimony layer to form an alloy phase, so that dendritic crystal formation can be effectively avoided, and a more stable electrode/electrolyte interface can be formed.
In one embodiment of the present invention, the lithium-containing compound is obtained by an alloying reaction of the following formula:
specifically, antimony on the surface of the reference electrode can react with lithium metal in the lithium ion battery to form LixAn Sb alloy. So that the antimony layer on the surface of the reference electrode can have the function of storing metallic lithium, and the metallic lithium can be better deposited on the surface of the reference electrode.
In one embodiment of the invention, the surface of the copper-antimony composite material is coated with an insulating layer.
Specifically, the surface of the copper-antimony composite material can be coated with an insulating layer, so that the contact between the electrolyte and the copper-antimony composite material can be reduced as much as possible, the influence of the electrolyte on lithium on the surface of the reference electrode is reduced, and the stability of the reference electrode is improved.
Optionally, the potential of the reference electrode is 0.8V (vs Li/Li +).
Specifically, the potential of the reference electrode can be 0.8V (vs Li/Li +), and the reference electrode can be well stabilized near the potential in the actual application process, so that the stable operation of the lithium ion battery of the three-electrode system is maintained.
Embodiments of the present invention also provide a three-electrode battery including the reference electrode according to embodiments of the present invention. The specific structural form and the working principle of the reference electrode have been described in detail in the foregoing embodiments, and are not described herein again.
According to the three-electrode battery provided by the embodiment of the invention, the diaphragm is arranged between the reference electrode and the anode of the three-electrode battery, and the diaphragm is arranged between the reference electrode and the cathode of the three-electrode battery; the reference electrode comprises a copper-antimony composite material, and a lithium-containing compound is deposited on the surface of the reference electrode through an alloying reaction. Therefore, the lithium can be well fixed on the surface of the reference electrode, the lithium can be uniformly deposited on the surface of the reference electrode, the lithium is not easy to react with the electrolyte in the subsequent circulation process, the lithium deposited on the surface of the reference electrode is effectively prevented from being damaged, and the lithium-ion battery has good structural stability and potential stability.
According to the three-electrode battery provided by the embodiment of the invention, the reference electrode with good structural stability and potential stability is added in the lithium ion battery. The electrode potential can be monitored during charging and discharging of the battery. During the charging and discharging process of the battery, the relative potential changes of the positive electrode, the negative electrode and the reference electrode can be respectively measured, so that the contribution of the positive electrode and the negative electrode to the voltage of the whole battery can be obtained. Meanwhile, the magnitude and the generation reason of the overpotential of the positive electrode and the negative electrode under different SOC conditions can be researched. Meanwhile, long-term monitoring can be carried out, the cause of degradation of the anode and the cathode is monitored, voice and control are carried out in time, and more serious failure of the lithium ion battery is prevented.
By arranging the reference electrode, the quick charging performance of the battery can be monitored, and the quick charging boundary of the battery is determined. The battery fast-charge boundary may be affected by parameters such as charge current, voltage, and temperature. It can determine the fast charge boundary by whether the lithium deposition occurs in the negative electrode during the fast charge. Therefore, the reference electrode can be arranged to monitor the positive and negative electrode points in the lithium ion battery, and the current battery state is determined based on the positive and negative electrode points, so that the potential of the negative electrode to Li/Li + is always greater than zero, and the performance degradation of the battery caused by the lithium precipitation of the negative electrode is prevented.
The embodiment of the invention also provides a vehicle which comprises the three-electrode battery. The specific structural form and the working principle of the three-electrode battery have been described in detail in the foregoing embodiments, and are not described herein again.
According to the vehicle provided by the embodiment of the invention, the diaphragm is arranged between the reference electrode of the three-electrode battery and the anode of the three-electrode battery, and the diaphragm is arranged between the reference electrode of the three-electrode battery and the cathode of the three-electrode battery; the reference electrode comprises a copper-antimony composite material, and a lithium-containing compound is deposited on the surface of the reference electrode through an alloying reaction. Therefore, the lithium can be well fixed on the surface of the reference electrode, the lithium can be uniformly deposited on the surface of the reference electrode, the lithium is not easy to react with the electrolyte in the subsequent circulation process, the lithium deposited on the surface of the reference electrode is effectively prevented from being damaged, and the lithium-ion battery has good structural stability and potential stability.
The reference electrode of the three-electrode battery, the three-electrode battery and the vehicle provided by the invention are described in detail, the principle and the implementation mode of the invention are explained by applying specific examples, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (10)
1. The reference electrode of the three-electrode battery is characterized in that a diaphragm is arranged between the reference electrode and the positive electrode of the three-electrode battery, and a diaphragm is arranged between the reference electrode and the negative electrode of the three-electrode battery; the reference electrode comprises a copper-antimony composite material, and a lithium-containing compound is deposited on the surface of the reference electrode through an alloying reaction.
2. The reference electrode according to claim 1, wherein the copper-antimony composite material is prepared by at least one of chemical plating of an antimony layer on the surface of a copper substrate, electroplating of an antimony layer on the surface of the copper substrate, and evaporation of an antimony layer on the surface of the copper substrate.
3. The reference electrode of claim 2, wherein the antimony layer has a thickness of 1-25 μm.
4. The reference electrode of claim 1, wherein the lithium-containing compound is LixSb(0<x≤3)。
5. The reference electrode of claim 1, wherein the lithium-containing compound is generated by an alloying reaction between the reference electrode and metallic lithium by charging between the positive electrode and the reference electrode of the three-electrode battery using a predetermined charging and discharging device.
6. The reference electrode according to claim 1 or 4 or 5, characterized in that the lithium-containing compound is obtained by an alloying reaction of the formula:
7. the reference electrode according to claim 1, wherein the surface of the copper-antimony composite material is coated with an insulating layer.
8. The reference electrode of claim 1, wherein the potential of the reference electrode is 0.8V (vs Li/Li +).
9. A three-electrode battery comprising a reference electrode according to any one of claims 1 to 8.
10. A vehicle comprising the three-electrode battery of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111649734.9A CN114335421A (en) | 2021-12-29 | 2021-12-29 | Reference electrode of three-electrode battery, and vehicle |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111649734.9A CN114335421A (en) | 2021-12-29 | 2021-12-29 | Reference electrode of three-electrode battery, and vehicle |
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| Publication Number | Publication Date |
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| CN114335421A true CN114335421A (en) | 2022-04-12 |
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| CN202111649734.9A Pending CN114335421A (en) | 2021-12-29 | 2021-12-29 | Reference electrode of three-electrode battery, and vehicle |
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- 2021-12-29 CN CN202111649734.9A patent/CN114335421A/en active Pending
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