CN111224162A - Method for pre-metallizing negative electrode of metal ion battery - Google Patents
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Abstract
本发明涉及锂离子电池领域，具体为一种金属离子电池负极预金属化的方法。金属离子电池的电解液中含有预金属化添加剂，所述预金属化添加剂为对应金属的金属盐。该金属盐在首次充电过程中在正极侧发生解离，解离后的阳离子可以嵌入负极材料，弥补金属阳离子在首次充电过程中的不可逆消耗；解离后的阴离子可以与正极物质发生化学反应，不影响电池的正常充放电。
The invention relates to the field of lithium ion batteries, in particular to a method for pre-metallizing a negative electrode of a metal ion battery. The electrolyte of the metal-ion battery contains a pre-metallization additive, and the pre-metallization additive is a metal salt of a corresponding metal. The metal salt dissociates on the positive electrode side during the first charging process, and the dissociated cations can be embedded in the negative electrode material to make up for the irreversible consumption of the metal cations during the first charging process; the dissociated anions can chemically react with the positive electrode material, Does not affect the normal charge and discharge of the battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a material and a method for an electrode electrochemical prelithiation electrode.
Background
Lithium ion battery technology has developed rapidly in recent years, and has been widely used for electric energy storage of small portable electronic devices due to its advantages of high energy density, long cycle life, low self-discharge rate, no memory effect, environmental friendliness, and the like. In recent years, in order to meet the demand of rapid development of new energy vehicles, smart power grids, distributed energy storage and other technologies, development of lithium ion batteries with high energy density, high safety and long service life becomes a research hotspot in the current energy storage field. The increase in energy density of batteries has mainly relied on the development of key electrode materials. A plurality of novel lithium ion battery negative electrode materials (such as silicon-carbon negative electrodes and the like) are found, have the specific capacity which is three times that of the commercial graphite negative electrode, and can greatly improve the energy density of the battery. However, these electrode materials generally have a low first turn coulombic efficiency, which causes problems for practical battery production.
The low coulombic efficiency in the first cycle is mainly because the electrolyte is decomposed on the negative electrode side during the first charging process of the battery, and a solid electrolyte film (SEI film) is irreversibly generated at the electrode interface. Such SEI films are mainly composed of organic and inorganic lithium compounds, and thus cause a certain amount of irreversible lithium loss. The pre-lithium intercalation technology is the most effective method for compensating lithium loss and improving the coulomb efficiency of the first circle at present. The commonly used lithium pre-intercalation methods are mainly physical, chemical and electrochemical methods. The physical method is that the cathode material is directly physically mixed with stable metal lithium powder (SLMP) or the cathode is in high-pressure extrusion contact with Li foil to realize the pre-lithium intercalation of the cathode; the chemical method is characterized in that a pre-embedded lithium additive is doped into a positive electrode material or a negative electrode material, and lithium is released by chemical change of the additive in the first charging process to compensate the first-turn irreversible lithium loss; the electrochemical method is to compensate lithium by half-cell discharge formed by a negative electrode and metallic lithium. These methods have compatibility and safety problems, which make them impractical. Gases may be generated while the positive electrode additive decomposes to release lithium, increasing the complexity of the battery manufacturing process, and a large number of unwanted residual products may also reduce the actual battery energy density; the anode material directly prelithiated by a physical method or an electrochemical method has problems of stability and safety.
It is an ideal pre-lithiation method to utilize this additional lithium storage capacity to compensate for the irreversible lithium loss from the first turn of the negative electrode by pre-lithiating the positive electrode active material. However, the materials used in the prior patent documents are mainly lithium nitride, lithium oxide, lithium sulfide, lithium ferrate, lithium manganate, etc., and there is a problem that the productivity is poor or the discharge product affects the performance.
Disclosure of Invention
The invention aims to provide an electrochemical prelithiation material and a production scheme aiming at the problem of low coulombic efficiency of a first circle of a metal ion (lithium, sodium, potassium and magnesium) battery negative electrode material.
The invention relates to the addition of a metal salt to the electrolyte, which metal salt can be dissociated on the positive side during the first charging process. The dissociated cations can be embedded into the negative electrode material to make up the irreversible consumption of the metal cations in the first charging process. The dissociated anion can chemically react with positive electrode substances (such as an aluminum foil current collector), and normal charge and discharge of the battery are not influenced.
The adopted specific technical scheme is as follows:
a method for pre-metallizing a negative electrode of a metal ion battery comprises the steps that electrolyte of the metal ion battery contains a pre-metallization additive, wherein the pre-metallization additive is metal salt of corresponding metal;
in the case of a lithium ion battery, the metal salt cation corresponding to the metal is Li+The anion is Br-、FSI-、Cl-、I-One or more than two of them; the positive active material is lithium vanadium phosphate, lithium manganate, lithium iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel manganese oxide, lithium vanadyl phosphate or lithium titanium phosphate;
in the case of a sodium ion battery, the cation of the metal salt corresponding to the metal is Na+The anion is Br-、FSI-、Cl-、I-One or more than two of them; the positive active substance is sodium cobaltate, sodium ferrite, sodium iron manganese copper, sodium vanadium phosphate, sodium vanadium fluorophosphate, sodium vanadyl phosphate or sodium titanium phosphate;
in the case of a potassium ion battery, the cation of the metal salt corresponding to the metal is K+The anion is Br-、FSI-、Cl-、I-One or more than two of them; the positive active material is vanadium pentoxide, potassium ferrocyanide, manganese dioxide, potassium vanadium phosphate, potassium titanium phosphate or potassium vanadium fluorophosphate;
in the case of a magnesium ion battery, the cation of the metal salt corresponding to the metal is Mg2+The anion is Br-、FSI-、Cl-、I-One or more than two of them; the positive active material is magnesium vanadate, vanadium pentoxide, molybdenum trioxide, manganese dioxide, titanium disulfide, molybdenum disulfide, magnesium ferric orthosilicate or magnesium nickel manganese.
The metal salt is dissociated on the positive electrode side in the first charging process, and dissociated cations can be embedded into the negative electrode material to make up the irreversible consumption of the metal cations in the first charging process; the dissociated anion can chemically react with the positive electrode substance, and normal charge and discharge of the battery are not influenced.
The addition amount of the metal salt is 25-50% of the total mass of the negative electrode active material in the negative electrode of the metal ion battery, and the addition amount of the metal salt is preferably 30-40%.
The negative active material is one or more than two of natural graphite, hard carbon, soft carbon, mesocarbon microbeads, silicon carbon, silicon oxide, red phosphorus, iron oxide, manganese dioxide, tin dioxide, cobaltosic oxide, niobium pentoxide and tin phosphide.
The positive electrode substance is one of an aluminum foil current collector, a nickel foil current collector or a titanium foil current collector.
The battery is charged for the first time at a rate of 0.05-0.1C at 25 ℃ to 3.8-4.8V, and then the constant-voltage current-limiting charging is stopped when the current is reduced to 0.002-0.0005C.
The invention has the advantages that:
1. method for expanding pre-embedded metal ions on metal ion battery cathode
2. Improving the overall energy density of the metal ion battery
3. Effectively prolonging the cycle life of the metal ion battery
4. Simplified manufacturing process of metal ion battery
Drawings
FIG. 1 is a first charge voltage-time curve of example 1
Detailed Description
Example 1: lithium ion battery using lithium bromide as prelithiation additive
And winding the copper foil coated with the Nippon Wuyu hard carbon on the two sides as a negative electrode, the aluminum foil coated with lithium vanadium phosphate on the two sides as a positive electrode and the celgard2325 as a diaphragm into a flexible package battery. Adding lithium ion battery electrolyte, wherein the solvent in the electrolyte is ethylene carbonate in volume ratio: propylene carbonate: dimethyl carbonate ═ 1: 1: 1, the lithium salt is lithium hexafluorophosphate, the concentration of the lithium salt is 1.0 mol, the prelithiation additive is lithium bromide, and the weight ratio of the addition amount of the lithium bromide to the hard carbon on the negative plate is 3: 1. the whole electrolyte is poured into the battery. After the battery is vacuum-packaged, the air bag is retained. The battery is charged at 25 ℃ under the multiplying power of 0.1C, and after the battery is charged to 4.8V, the constant-voltage current-limiting charging is cut off when the current is reduced to 0.001C.
Example 2: sodium ion battery using sodium bromide as prelithiation additive
And winding the copper foil coated with the Nippon Wuyu hard carbon on the two sides as a negative electrode, the aluminum foil coated with lithium vanadium phosphate on the two sides as a positive electrode and the celgard2325 as a diaphragm into a flexible package battery. Adding sodium ion battery electrolyte, wherein the solvent in the electrolyte is ethylene carbonate: propylene carbonate: dimethyl carbonate ═ 1: 1: 1, sodium salt is sodium hexafluorophosphate, the concentration of the sodium salt is 1.0 mol, the prelithiation additive is sodium bromide, and the weight ratio of the addition amount of the sodium bromide to the hard carbon on the negative plate is 3: 1. the whole electrolyte is poured into the battery. After the battery is vacuum-packaged, the air bag is retained. The battery is charged under the multiplying power of 0.1C, after the battery is charged to 3.8V, the constant-voltage current-limiting charging is cut off when the current is reduced to 0.001C.
Example 3: magnesium ion battery using magnesium bromide as premagnesization additive
And winding the copper foil coated with the Wuyu Nippon hard carbon on both sides as a negative electrode, the aluminum foil coated with the magnesium vanadate on both sides as a positive electrode and the celgard2325 as a diaphragm into a flexible package battery. Adding magnesium ion battery electrolyte, wherein the solvent in the electrolyte is ethylene carbonate: propylene carbonate: dimethyl carbonate ═ 1: 1: 1, magnesium salt is bis (trifluoromethyl) sulfonyl imide magnesium, the concentration of the magnesium salt is 1.0 mol, the premagnesization additive is magnesium bromide, and the weight ratio of the addition amount of the magnesium bromide to the hard carbon on the negative plate is 3: 1. the whole electrolyte is poured into the battery. After the battery is vacuum-packaged, the air bag is retained. The battery is charged under the multiplying power of 0.1C, after the battery is charged to 3.7V, the constant-voltage current-limiting charging is cut off when the current is reduced to 0.001C.
Example 4: lithium ion battery using lithium bis (fluorosulfonyl) imide as prelithiation additive
And winding the copper foil coated with the Nippon Wuyu hard carbon on the two sides as a negative electrode, the aluminum foil coated with lithium vanadium phosphate on the two sides as a positive electrode and the celgard2325 as a diaphragm into a flexible package battery. Adding lithium ion battery electrolyte, wherein the solvent in the electrolyte is ethylene carbonate: propylene carbonate: dimethyl carbonate ═ 1: 1: 1, the lithium salt is lithium hexafluorophosphate, the concentration of the lithium salt is 1.0 mol, the prelithiation additive is lithium chloride, and the weight ratio of the addition amount of the lithium chloride to the hard carbon on the negative plate is 2: 1. the whole electrolyte is poured into the battery. After the battery is vacuum-packaged, the air bag is retained. The battery is charged at 25 ℃ under the multiplying power of 0.1C, and after the battery is charged to 4.35V, the constant-voltage current-limiting charging is cut off when the current is reduced to 0.001C.
Example 5: lithium ion battery using lithium bromide as prelithiation additive
The wuyu hard carbon in japan in example 1 was changed to the homemade hard carbon, and the other conditions were not changed.
Example 6: sodium ion battery using sodium bromide as pre-sodium additive
The wuyu hard carbon in japan in example 2 was changed to the homemade hard carbon, and the other conditions were not changed.
Example 7: magnesium ion battery using magnesium bromide as premagnesization additive
The wuyu hard carbon in japan in example 3 was changed to the homemade hard carbon, and the other conditions were not changed.
Example 8: potassium ion battery using potassium bromide as pre-potassizing additive
The wuyu hard carbon in japan in example 4 was changed to the homemade hard carbon, and the other conditions were not changed.
Example 9: sodium ion battery using sodium chloride as pre-sodium additive
The pre-sodium additive of example 1 was changed to sodium chloride, and the other conditions were unchanged.
Example 10: lithium ion battery using lithium hydride as prelithiation additive
The prelithiation additive of example 1 was changed to lithium hydride, and the other conditions were unchanged.
Example 11: lithium ion battery using lithium amide as prelithiation additive
The prelithiation additive of example 1 was changed to lithium amide, with the other conditions unchanged.
Example 12: sodium ion battery using sodium hydride as pre-sodium additive
The pre-sodium additive of example 1 was changed to sodium hydride, and the other conditions were unchanged.
Example 13: lithium ion battery using lithium hydride as prelithiation additive
The prelithiation additive of example 1 was changed to lithium hydride, and the other conditions were unchanged.
Example 14: lithium ion super capacitor using lithium bromide as pre-lithiation additive
Copper foil coated with Wuyu Japan hard carbon on both sides is used as a negative electrode, aluminum foil coated with Coloray YP-50F active carbon on both sides is used as a positive electrode, celgard2325 is used as a diaphragm, and the positive electrode and the negative electrode are wound into a flexible package battery. Adding lithium ion battery electrolyte, wherein the solvent in the electrolyte is ethylene carbonate: propylene carbonate: dimethyl carbonate ═ 1: 1: 1, the lithium salt is lithium hexafluorophosphate, the concentration of the lithium salt is 1.0 mol, the prelithiation additive is lithium bromide, and the weight ratio of the addition amount of the lithium bromide to the hard carbon on the negative plate is 3: 1. the whole electrolyte is poured into the battery. After the battery is vacuum-packaged, the air bag is retained. The battery is charged at 25 ℃ under the multiplying power of 0.1C, and after the battery is charged to 4.3V, the constant-voltage current-limiting charging is cut off when the current is reduced to 0.001C.
Example 15: sodium ion super capacitor using sodium bromide as pre-lithiation additive
Copper foil coated with Wuyu Japan hard carbon on both sides is used as a negative electrode, aluminum foil coated with Coloray YP-50F active carbon on both sides is used as a positive electrode, celgard2325 is used as a diaphragm, and the positive electrode and the negative electrode are wound into a flexible package battery. Adding sodium ion battery electrolyte, wherein the solvent in the electrolyte is ethylene carbonate: propylene carbonate: dimethyl carbonate ═ 1: 1: 1, sodium salt is sodium hexafluorophosphate, the concentration of the sodium salt is 1.0 mol, the pre-sodium additive is sodium bromide, and the weight ratio of the addition amount of the sodium bromide to the hard carbon on the negative plate is 3: 1. the whole electrolyte is poured into the battery. After the battery is vacuum-packaged, the air bag is retained. The battery is charged at 25 ℃ under the multiplying power of 0.1C, and after the battery is charged to 3.8V, the constant-voltage current-limiting charging is cut off when the current is reduced to 0.001C.
Comparative examples 1 to 14
In addition to examples 1 to 14, no additive was added, and the other conditions were unchanged.
After the prelithiation additive is added in the embodiment, in the first charging process, the prelithiation additive is decomposed to compensate the irreversible capacity of the negative electrode in the first charging process, and compared with a comparative example, the utilization rate of the active material of the positive electrode is improved, so that the specific energy of the battery is improved. TABLE 1
| Name (R) | First coulombic efficiency | Capacity retention rate at 1000 cycles | Specific energy/Wh/kg |
| Example 1 | 50 | 99.8％ | 190 |
| Example 2 | 51 | 98.8％ | 120 |
| Example 3 | 52 | 99.6％ | 100 |
| Example 4 | 60 | 99.5％ | 120 |
| Example 5 | 61 | 99.7％ | 190 |
| Example 6 | 59 | 99.0％ | 120 |
| Example 7 | 57 | 99.6％ | 100 |
| Example 8 | 61 | 99.5％ | 120 |
| Example 9 | 55 | 99.1％ | 180 |
| Example 10 | 45 | 99.7％ | 180 |
| Example 11 | 68 | 99.9％ | 180 |
| Example 12 | 62 | 99.6％ | 120 |
| Example 13 | 53 | 99.4％ | 180 |
| Example 14 | 56 | 99.5％ | 180 |
| Example 15 | 57 | 99.5％ | 90 |
| Comparative example 1 | 50 | 91.8％ | 90 |
| Comparative example 2 | 51 | 91.8％ | 60 |
| Comparative example 3 | 52 | 92.6％ | 50 |
| Comparative example 4 | 60 | 91.5％ | 60 |
| Comparative example 5 | 61 | 90.7％ | 90 |
| Comparative example 6 | 59 | 93.0％ | 60 |
| Comparative example 7 | 57 | 92.6％ | 50 |
| Comparative example 8 | 61 | 91.5％ | 60 |
| Comparative example 9 | 55 | 93.1％ | 90 |
| Comparative example 10 | 45 | 94.7％ | 90 |
| Comparative example 11 | 68 | 96.9％ | 90 |
| Comparative example 12 | 62 | 95.6％ | 60 |
| Comparative example 13 | 53 | 97.4％ | 90 |
| Comparative example 14 | 56 | 94.5％ | 60 |
Claims (6)
1. A method for pre-metallizing a negative electrode of a metal-ion battery is characterized by comprising the following steps:
the electrolyte of the metal ion battery contains a pre-metallization additive, wherein the pre-metallization additive is a metal salt of a corresponding metal;
in the case of a lithium ion battery, the metal salt cation corresponding to the metal is Li+The anion is Br-、FSI-、Cl-、I-One or more than two of them; the positive active material is lithium vanadium phosphate, lithium manganate, lithium iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel manganese oxide, lithium vanadyl phosphate or lithium titanium phosphate;
in the case of a sodium ion battery, the cation of the metal salt corresponding to the metal is Na+The anion is Br-、FSI-、Cl-、I-One or more than two of them; the positive active substance is sodium cobaltate, sodium ferrite, sodium iron manganese copper, sodium vanadium phosphate, sodium vanadium fluorophosphate, sodium vanadyl phosphate or sodium titanium phosphate;
in the case of a potassium ion battery, the cation of the metal salt corresponding to the metal is K+The anion is Br-、FSI-、Cl-、I-One or more than two of them; the positive active material is vanadium pentoxide, potassium ferrocyanide, manganese dioxide, potassium vanadium phosphate, potassium titanium phosphate or potassium vanadium fluorophosphate;
in the case of a magnesium ion battery, the cation of the metal salt corresponding to the metal is Mg2+The anion is Br-、FSI-、Cl-、I-One or more than two of them; the positive active material is magnesium vanadate, vanadium pentoxide, molybdenum trioxide, manganese dioxide, titanium disulfide, molybdenum disulfide, magnesium ferric orthosilicate or magnesium nickel manganese.
2. The method of claim 1, wherein: the metal salt is dissociated on the positive electrode side in the first charging process, and dissociated cations can be embedded into the negative electrode material to make up the irreversible consumption of the metal cations in the first charging process; the dissociated anion can chemically react with the positive electrode substance, and normal charge and discharge of the battery are not influenced.
3. The method of claim 1, wherein: the addition amount of the metal salt is 25-50% of the total mass of the negative electrode active material in the negative electrode of the metal ion battery, and the addition amount of the metal salt is preferably 30-40%.
4. A method according to claim 3, characterized by: the negative active material is one or more than two of natural graphite, hard carbon, soft carbon, mesocarbon microbeads, silicon carbon, silicon oxide, red phosphorus, iron oxide, manganese dioxide, tin dioxide, cobaltosic oxide, niobium pentoxide and tin phosphide.
5. The method of claim 2, wherein: the positive electrode substance is one of an aluminum foil current collector, a nickel foil current collector or a titanium foil current collector.
6. The method of claim 1, wherein: the battery is charged for the first time at a rate of 0.05-0.1C at 25 ℃ to 3.8-4.8V, and then the constant-voltage current-limiting charging is stopped when the current is reduced to 0.002-0.0005C.
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| CN112687846A (en) * | 2020-12-29 | 2021-04-20 | 天目湖先进储能技术研究院有限公司 | Pre-metallization method of electrode |
| CN112687846B (en) * | 2020-12-29 | 2022-12-02 | 天目湖先进储能技术研究院有限公司 | Pre-metallization method of electrode |
| CN113046768A (en) * | 2021-03-15 | 2021-06-29 | 东北师范大学 | Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery |
| CN113046768B (en) * | 2021-03-15 | 2023-07-21 | 东北师范大学 | Potassium fluorovanadyl phosphate, preparation method and application thereof, and potassium ion battery |
| CN113113235A (en) * | 2021-04-15 | 2021-07-13 | 中国科学院电工研究所 | Sodium ion capacitor and negative electrode pre-sodium treatment method thereof |
| CN113113235B (en) * | 2021-04-15 | 2022-11-15 | 中国科学院电工研究所 | Sodium ion capacitor and negative electrode pre-sodium treatment method thereof |
| CN113178548A (en) * | 2021-04-27 | 2021-07-27 | 清华大学深圳国际研究生院 | Pre-sodium graphene negative pole piece, preparation method thereof and sodium ion battery |
| CN114420936A (en) * | 2022-03-29 | 2022-04-29 | 太原科技大学 | A kind of nitrogen-doped layer-extended graphite/tin phosphide multilayer composite material and preparation method thereof |
| CN114420936B (en) * | 2022-03-29 | 2022-05-27 | 太原科技大学 | Nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material and preparation method thereof |
| WO2024065276A1 (en) * | 2022-09-28 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Secondary battery, manufacturing method therefor, and electric apparatus |
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