CN118315682A - Third electrode for removing dendrite of battery and removing method - Google Patents
Third electrode for removing dendrite of battery and removing method Download PDFInfo
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- CN118315682A CN118315682A CN202410517348.1A CN202410517348A CN118315682A CN 118315682 A CN118315682 A CN 118315682A CN 202410517348 A CN202410517348 A CN 202410517348A CN 118315682 A CN118315682 A CN 118315682A
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- battery
- electrode
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- lithium
- cavity
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- 210000001787 dendrite Anatomy 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 108
- 229910052744 lithium Inorganic materials 0.000 claims description 106
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 210000004027 cell Anatomy 0.000 claims description 7
- 230000002000 scavenging effect Effects 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 230000005684 electric field Effects 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- -1 for example Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000002641 lithium Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Abstract
The embodiment of the invention discloses a third electrode for removing dendrites of a battery and a removing method. A third electrode for removing dendrites of a battery, the battery comprising a battery positive electrode, a battery electrolyte, a battery separator, and a battery negative electrode, the third electrode comprising a cavity and an electrode pad; the cavity comprises a detachable upper cavity and a detachable lower cavity which are communicated, the upper cavity is provided with at least one opening, the battery electrolyte can flow through the opening and the cavity, the opening is made of an electrode diaphragm, an electrode plate is arranged in the lower cavity, and the lower cavity is made of an electrode insulating film. The method provided by the invention can thoroughly eliminate the dendrite of the battery, prolong the service life of the battery by many times, greatly reduce the cost, and has wide application range and good popularization and application value.
Description
Technical Field
The embodiment of the invention relates to the technical field of battery dendrites, in particular to a third electrode for removing battery dendrites and a removing method.
Background
Lithium dendrites refer to an abnormal image in which lithium ions are not inserted into a negative electrode material in a negative electrode during charging of a lithium battery, but are precipitated on the surface of the negative electrode in the form of metallic lithium. The method is easy to occur in the processes of low temperature, quick charge, overcharge and the like. The precipitated lithium metal does not form a flat coating but exists in the form of dendrites, which are called lithium dendrites.
Dendrite formation can lead to several problems: 1. capacity loss: dendrites may pierce the separator of the battery, resulting in short circuits and capacity loss. 2. Internal short circuit: dendrites may penetrate the separator of the battery, causing internal short circuits, thereby inducing thermal runaway and fire. 3. The service life is shortened: dendrite formation can reduce the useful life of the battery.
In view of this, reducing dendrite formation, or scavenging generated dendrites, is of great importance to improve the performance and safety of the battery.
Disclosure of Invention
Therefore, the embodiment of the invention provides a third electrode for removing dendrites of a battery and a removing method.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
According to a first aspect of embodiments of the present invention, there is provided a third electrode for removing dendrites of a battery, the battery including a battery positive electrode, a battery electrolyte, a battery separator, and a battery negative electrode, the third electrode including a cavity and an electrode pad; the cavity comprises a detachable upper cavity and a detachable lower cavity which are communicated, the upper cavity is provided with at least one opening, the battery electrolyte can flow through the opening and the cavity, the opening is made of an electrode diaphragm, an electrode plate is arranged in the lower cavity, and the lower cavity is made of an electrode insulating film.
Further, the battery dendrites include lithium dendrites in lithium batteries, sodium dendrites in sodium batteries, or iron dendrites in lithium iron phosphate batteries.
Further, the electrode plate is made of the same material as the battery cathode, and the electrode diaphragm is made of the same material as the battery diaphragm.
Further, an opening is arranged on the inner wall of the upper cavity.
According to a second aspect of embodiments of the present invention, there is provided a circuit for scavenging battery dendrites, the circuit comprising: the third electrode, the direct current power supply and the control switch of any one of the above, wherein the control switch is used for controlling the on-off of a circuit, the positive electrode of the direct current power supply is connected with the negative electrode of the battery, and the negative electrode of the direct current power supply is connected with the electrode plate of the third electrode.
According to a third aspect of embodiments of the present invention, there is provided a method of removing battery dendrites based on a circuit as described above, the method comprising:
After the battery is completely discharged and all loads are disconnected, the third electrode is arranged between the battery diaphragm and the battery cathode, the opening part of the third electrode is soaked in battery electrolyte, the control switch is closed, dendrites attached to the battery cathode are dissolved in the battery electrolyte, and the dendrites pass through the opening part to reach the electrode plate under the action of an electric field to become new dendrites attached to the electrode plate.
Further, the voltage of the direct current power supply is 3.7V.
Further, the battery negative electrode is divided into a wet section and a dry section, the negative electrode lead is arranged at the end of the dry section, the wet section is immersed in the battery electrolyte, and the dry section is exposed to the outside and is not in contact with the battery electrolyte.
Further, the method further comprises: and removing the lower cavity of the third electrode, and removing dendrites attached to the electrode plate.
Further, the method further comprises: opening the opening on the inner wall of the cavity on the third electrode to supplement electrolyte and lithium ions to the battery.
The embodiment of the invention has the following advantages:
1. completely eliminates lithium dendrite and eliminates fire disaster caused by spontaneous combustion of the lithium battery.
The easy spontaneous ignition is the most fatal defect of the lithium battery, and lithium dendrites are the root cause of spontaneous ignition of the lithium battery. The method can thoroughly prevent spontaneous combustion of the lithium battery.
2. The service life of the lithium battery is prolonged by many times, so that the lithium battery has the same service life as the equipment using the lithium battery.
The biggest disadvantage of the current electric car compared with the oil car in use cost is that the service life of the electric car battery is too short, three or four years less, and five or six years more batteries are scrapped. This greatly limits the popularization of electric vehicles. The first method for prolonging the service life of the lithium battery is that before each time or a plurality of times of charging, the control system firstly discharges the battery completely, and disconnects all loads of the battery, then the control switch is switched on, the third electrode power supply starts to work, and lithium dendrites on the cathode of the lithium battery are thoroughly removed. The whole cleaning process is automatically completed by the system. The second method of the technology is to perform two works of 'cleaning lithium dendrite on the third electrode plate' and 'supplementing lithium battery electrolyte and lithium ions' on the whole car battery after the lithium battery is used for a long time (such as three to five years of trolley battery use). The specific operation is as follows: the lower part of the third electrode (lower part of red dotted line in fig. 1) is removed, lithium dendrites attached to the third electrode pad are removed, and then electrolyte and lithium ions are replenished into the lithium battery through the opened upper opening of the third electrode. The two methods can be repeated for a plurality of times, and the lithium battery and the equipment (such as an electric automobile and the like) using the lithium battery can have the same service life.
3. The method enables the existing liquid lithium battery to have more cost advantages compared with future solid lithium batteries.
Although the future solid-state lithium battery has the advantages of high energy density and safety and reliability, the cost of the solid-state lithium battery is many times higher than that of the same liquid-state lithium battery, and the technology is still not mature. By using the method of the invention, the service life of the liquid lithium battery is greatly prolonged, the use cost is greatly reduced, and the method can completely replace the solid lithium battery.
4. The method can also be used for removing lithium dendrites in solid state batteries.
The solid-state battery also produces lithium dendrites, and the method can also remove lithium dendrites in the solid-state battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It will be apparent to those of ordinary skill in the art that the drawings in the following description are exemplary only and that other implementations can be obtained from the extensions of the drawings provided without inventive effort.
Fig. 1 is a schematic structural diagram of a third electrode according to an embodiment of the present invention;
Fig. 2 is a schematic structural view of a third electrode according to an embodiment of the present invention mounted on a battery;
FIG. 3 is a schematic diagram of a third electrode for removing dendrites from a battery according to an embodiment of the present invention;
fig. 4 is a schematic structural diagram of a battery anode according to an embodiment of the present invention;
fig. 5 is a graph of internal resistance versus time of a lithium battery according to an embodiment of the present invention.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Battery dendrites include dendrites generated in various batteries, such as lithium dendrites in lithium batteries, sodium dendrites in sodium batteries, iron dendrites in lithium iron phosphate batteries, and the like, including not only liquid batteries but also solid batteries. The present invention is illustrated with lithium dendrites in a liquid lithium battery as an example.
Example 1
The present embodiment provides a third electrode for scavenging lithium dendrites in a lithium battery. Referring to fig. 1, the third electrode includes a cavity, a third electrode pad, and a lead. Wherein:
the cavity comprises the upper cavity and the lower cavity that are linked together, and upper cavity and lower cavity can integrated into one piece, also can adopt the mode of freely dismantling to connect. As an example, the upper cavity and the lower cavity are connected by adopting threads conventional in the art, and the free disassembly of the upper cavity and the lower cavity can be realized by arranging internal threads on the inner side of the lower end of the upper cavity and arranging external threads matched with the internal threads on the outer side of the upper end of the lower cavity.
The upper cavity is provided with at least one opening part through which lithium battery electrolyte can flow with the cavity, and the opening part is made of a third electrode diaphragm. The third electrode separator may employ a separator material commonly used for lithium batteries, for example, a woven film, a nonwoven film (nonwoven fabric), a microporous film, a composite film, separator paper, a laminate film, or the like. Further preferably, the material of the upper cavity except the opening is an electrode insulating film. The electrode insulating film mainly provides insulating properties, and is generally made of a polymer or other high insulating material, for example, polypropylene (PP), polyethylene (PE), polyester (PET), and other materials. Further preferably, an opening which can be freely closed or opened is also arranged on the inner wall of the upper cavity, and electrolyte and lithium ions can be supplemented into the lithium battery through the opening.
The lower cavity is made of a third electrode insulating film which is impermeable to electrolyte, and the third electrode insulating film is used for storing lithium atoms attached to the cathode of the third electrode and preventing the lithium atoms from diffusing outside the third electrode, and can be made of other materials such as polypropylene (PP), polyethylene (PE), polyester (PET) and the like. And a third electrode plate and a lead are arranged in the lower cavity, wherein the lead is arranged at the end part of the third electrode plate and is used for connecting the third electrode plate with other parts. The third electrode plate and the lead are made of the same materials as the negative electrode and the lead of the lithium battery. In some specific embodiments, the third electrode pad and the lithium battery negative electrode are both graphite. The third electrode pad functions to attach lithium atoms thereto to form new lithium dendrites.
Example 2
The present embodiment provides a circuit for scavenging lithium dendrites in a lithium battery. Referring to fig. 2, the circuit comprises a third electrode, a lithium battery cathode, a third electrode direct current power supply and a third electrode control switch which are connected through wires, wherein the third electrode control switch is used for controlling the on-off of the circuit, the positive electrode of the third electrode direct current power supply is connected with the lithium battery cathode, and the negative electrode of the third electrode direct current power supply is connected with a lead wire at the end part of a third electrode plate.
The method for installing the circuit comprises the following steps:
And installing a third electrode between the lithium battery diaphragm and the lithium battery negative electrode, wherein the upper cavity of the third electrode is soaked in electrolyte of the lithium battery, and specifically, the opening part of the upper wall body is completely soaked in the electrolyte so as to ensure that the electrolyte is communicated between the lithium battery and the third electrode. In some preferred embodiments, the voltage of the third electrode dc power supply is 3.7V.
Example 3
The present embodiment provides a method for scavenging lithium dendrites in a lithium battery:
After the battery is completely discharged and all loads are disconnected, a third electrode is arranged between a battery diaphragm and a battery cathode, the opening of a cavity on the third electrode is soaked in battery electrolyte, a third electrode control switch is closed, after the lithium battery is completely discharged and all loads are disconnected, a third electrode direct current power supply is closed, lithium atoms (lithium dendrites) attached to the lithium battery cathode lose one electron and become positively charged lithium ions, the positively charged lithium ions are dissolved in the electrolyte, and pass through the third electrode diaphragm to reach a third electrode plate under the action of an electric field. The lithium ions get an electron on the third electrode pad and become lithium atoms (new lithium dendrites) attached to the third electrode pad. The reaction formula is as follows:
On the lithium battery negative electrode:
Li-e=li + (lithium atom loses one electron to become lithium ion)
On the third electrode pad:
Li + +e=li (lithium ion gets one electron to become lithium atom)
This process is to transfer lithium dendrites on the negative electrode of the lithium battery to the plate of the third electrode.
When the volume of the lithium dendrite attached to the third electrode plate exceeds a certain amount, the lower cavity of the third electrode (the lower part of the red dotted line in fig. 1) can be conveniently detached, the lithium dendrite attached to the third electrode plate is removed and then is reloaded to the original place, and the part can be replaced. Because the negative electrode material of the lithium battery is graphite, the method can not damage the negative electrode of the lithium battery.
Before the lower cavity of the third electrode is restored, the opening on the inner wall of the upper cavity of the third electrode can be opened to supplement electrolyte and lithium ions for the lithium battery.
The method can also remove dendrites in various batteries such as iron dendrites in the lithium iron phosphate battery, sodium dendrites in the sodium battery and the like.
The third electrode is located in the lower chamber of the red dotted line, and is positioned in a container for storing lithium dendrites. Each lithium battery may be fitted with one or more such containers as desired.
In some preferred embodiments, the negative electrode of the lithium battery is mostly immersed in the electrolyte (lower portion of the white dotted line in fig. 4), referred to as the wet section. A small portion (upper portion of the white dotted line in fig. 4) is exposed to the outside without contact with the electrolyte, called a dry section, to which the negative electrode lead of the lithium battery is connected. The drying section is provided to isolate the negative electrode lead from the electrolyte. When the operation of removing the lithium dendrites is carried out, the negative electrode of the lithium battery is positively charged, and if a negative electrode lead made of metal is directly contacted with electrolyte, metal atoms (generally copper or lead) in the lead are ionized into positively charged metal ions, and the positively charged metal ions enter the electrolyte, so that the electrolyte is polluted and the negative electrode lead is corroded.
Test case
Test for removing lithium dendrites
1. Parameters of the test apparatus:
lithium battery variety: a polymer lithium battery; lithium battery voltage: 3.7V; lithium battery capacity: 10000mAh; internal resistance of lithium battery: 46mΩ; area of negative electrode plate of lithium battery: 10cm×94 cm=940 cm 2; area of the electrode plate where the third electrode contacts the negative electrode of the lithium battery: 1cm x 94cm = 94cm 2; third electrode dc power supply voltage: 3.7V; 22 lithium batteries were used for each test. The test times are 20 times, and all new lithium batteries with the same type and produced by the same manufacturer are used each time.
2. Artificial formation of lithium dendrites
After trial and error, the lithium cells were charged with 4.2v dc at 0 ℃ for 5 minutes, all 22 cells were slightly bulging. 2 of them were disassembled, and large-area lithium dendrite deposition occurred on the negative electrode plate.
3. Lithium dendrite removal test
The lithium battery is fully discharged and all loads of the lithium battery are disconnected. A third electrode was placed between the negative electrode of the lithium battery and the separator of the lithium battery according to fig. 2. And the third electrode control switch is closed, and the internal resistance of the lithium battery is measured every 3 minutes. The following curves were obtained by taking the average of 20 data. The capacity of each cell before and after removal of lithium dendrites was compared and after removal of lithium dendrites, the capacity of the lithium cell was restored to 99.86% before removal. After each test was completed, 5 lithium batteries were disassembled and observed, and all lithium dendrites on the negative electrode plate of the lithium battery disappeared.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A third electrode for removing dendrites from a battery, the battery comprising a battery positive electrode, a battery electrolyte, a battery separator, and a battery negative electrode, wherein the third electrode comprises a cavity and an electrode pad; the cavity comprises a detachable upper cavity and a detachable lower cavity which are communicated, the upper cavity is provided with at least one opening, the battery electrolyte can flow through the opening and the cavity, the opening is made of an electrode diaphragm, an electrode plate is arranged in the lower cavity, and the lower cavity is made of an electrode insulating film.
2. The third electrode for scavenging cell dendrites of claim 1 wherein said cell dendrites comprise lithium dendrites in a lithium cell, sodium dendrites in a sodium cell or iron dendrites in a lithium iron phosphate cell.
3. The third electrode for removing dendrites from a battery of claim 1 wherein said electrode pad is of the same material as the negative electrode of the battery and said electrode separator is of the same material as the separator of the battery.
4. The third electrode for removing dendrites from a battery of claim 1 wherein said upper cavity has an opening in an inner wall thereof.
5. A circuit for removing battery dendrites, the circuit comprising:
The third electrode, a direct current power supply and a control switch according to any one of claims 1-4, wherein the control switch is used for controlling on-off of a circuit, a positive electrode of the direct current power supply is connected with a negative electrode of a battery, and a negative electrode of the direct current power supply is connected with an electrode plate of the third electrode.
6. A method of removing battery dendrites based on the circuit of claim 5, the method comprising:
After the battery is completely discharged and all loads are disconnected, the third electrode is arranged between the battery diaphragm and the battery cathode, the opening part of the third electrode is soaked in battery electrolyte, the control switch is closed, dendrites attached to the battery cathode are dissolved in the battery electrolyte, and the dendrites pass through the opening part to reach the electrode plate under the action of an electric field to become new dendrites attached to the electrode plate.
7. The method of claim 6, wherein the dc power source has a voltage of 3.7V.
8. The method of claim 6, wherein the battery negative electrode is divided into a wet section and a dry section, and the negative electrode lead is disposed at an end of the dry section, the wet section is immersed in the battery electrolyte, and the dry section is exposed to the outside and is not in contact with the battery electrolyte.
9. The method of claim 6, wherein the method further comprises: and removing the lower cavity of the third electrode, and removing dendrites attached to the electrode plate.
10. The method according to claim 9, wherein the method further comprises: opening the opening on the inner wall of the cavity on the third electrode to supplement electrolyte and lithium ions to the battery.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118315682A true CN118315682A (en) | 2024-07-09 |
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