CN114824241A - Device and method for carrying out liquid-phase pre-lithiation treatment on silicon monoxide negative electrode material - Google Patents
Device and method for carrying out liquid-phase pre-lithiation treatment on silicon monoxide negative electrode material Download PDFInfo
- Publication number
- CN114824241A CN114824241A CN202210439347.0A CN202210439347A CN114824241A CN 114824241 A CN114824241 A CN 114824241A CN 202210439347 A CN202210439347 A CN 202210439347A CN 114824241 A CN114824241 A CN 114824241A
- Authority
- CN
- China
- Prior art keywords
- kettle
- solvent
- organic solvent
- lithium
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000007791 liquid phase Substances 0.000 title claims abstract description 29
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 28
- 238000006138 lithiation reaction Methods 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 75
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002904 solvent Substances 0.000 claims abstract description 62
- 238000002156 mixing Methods 0.000 claims abstract description 56
- 239000003960 organic solvent Substances 0.000 claims abstract description 49
- 238000011084 recovery Methods 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 19
- 238000009835 boiling Methods 0.000 claims abstract description 14
- 239000012442 inert solvent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 23
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 6
- 230000008569 process Effects 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000010419 fine particle Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 101100298222 Caenorhabditis elegans pot-1 gene Proteins 0.000 description 1
- 101100298225 Caenorhabditis elegans pot-2 gene Proteins 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a device and a method for carrying out liquid-phase pre-lithiation treatment on a silicon monoxide negative electrode material, wherein the device comprises a solvent kettle for dissolving a lithium source in an organic solvent, a mixing kettle for mixing the silicon monoxide negative electrode material and the lithium source, and a solvent recovery kettle for recovering the organic solvent; the device is used for carrying out liquid-phase pre-lithiation treatment on the silicon oxide negative electrode material, the potential safety hazard problem caused by volatilization of the organic solvent in the liquid-phase method pretreatment process can be effectively solved, the organic solvent can be recycled, the production cost can be obviously reduced, and the device has good economic benefit and industrial application prospect. In addition, the organic solvent selected by the invention is a high-boiling point inert solvent which does not react with lithium metal, so that the lithium metal keeps 0 valence and has strong reducibility, and the high-boiling point inert solvent only plays a role in heat conduction and lithium metal dispersion, so that the lithium metal is melted and dispersed in the solvent into fine particles and can fully react with the silicon monoxide negative electrode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a device and a method for carrying out liquid-phase pre-lithiation treatment on a silicon oxide negative electrode material.
Background
The traditional graphite cathode can not meet the requirement of higher energy density in the design of a battery cell, and the silicon oxide cathode has higher specific capacity and is considered as a new generation cathode material with the most prospect, but has some defects and cannot be applied in a large scale. When the silicon monoxide negative electrode is embedded with lithium, the expansion reaches 200 percent, the pulverization failure of the material is easily caused in the circulating process, a large amount of irreversible lithium silicate is formed during the first lithium embedding, the first effect is lower, and the conductivity of the material is poorer.
In order to improve the first coulombic efficiency, the lithium ion battery can be subjected to pre-lithiation treatment, and the strong reducibility of metal lithium is utilized to be combined with active oxygen in SiO so as to generate more reversible silicon. However, the lithium metal is more active and is easy to react with oxygen and water in the air, and the production process has strict requirements. At present, methods for carrying out pre-lithiation treatment on a SiO/C negative electrode material are mainly divided into a gas phase method, a solid phase method and a liquid phase method, wherein: the temperature required by the gasification of the lithium source by the vapor phase method is up to 1340 ℃, and the requirements on a reaction device are high in a vacuum environment; the reaction energy barrier between the solid-phase method lithium source and SiO/C is high, high-temperature conditions are needed, and the excessive growth of Si crystal grain size is easily caused; the liquid phase method requires dissolving a lithium source in an organic solvent, and then mixing the lithium source with a negative electrode material. Compared with a gas phase method and a solid phase method, the liquid phase method has relatively low treatment temperature and is easy to realize industrial production.
However, the existing liquid phase method has the following defects: (1) most of lithium salts are selected as lithium sources, and the lithium salts are dissolved in an organic solvent to obtain a lithium-containing solvent; or selecting metal lithium as a lithium source, and obtaining a lithium-containing solvent through the reaction of the metal lithium and an organic solvent; the disadvantage is that the obtained lithium-containing solvent has +1 valence of lithium and no reducibility; (2) in the prior art, the used organic solvent is volatile and has certain toxicity, so that operators have certain potential safety hazards in the operation process.
Disclosure of Invention
The invention aims to provide a device and a method for carrying out liquid-phase pre-lithiation treatment on a silicon oxide negative electrode material, so as to solve the problems of reduction of lithium reducibility in the process of pretreating the silicon oxide material by using a liquid-phase method and potential safety hazards caused by volatilization of an organic solvent and the like in the prior art; meanwhile, the device can provide a good oxygen-free and water-free environment, and ensures the smooth implementation of the pre-lithiation treatment.
To solve the deficiencies in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a device for carrying out liquid-phase pre-lithiation treatment on a silicon monoxide negative electrode material comprises a solvent kettle for dissolving a lithium source in an organic solvent, a mixing kettle for mixing the silicon monoxide negative electrode material and the lithium source, and a solvent recovery kettle for recovering the organic solvent; the top of the mixing kettle is provided with a feed inlet and a solvent volatilization outlet, and the bottom of the mixing kettle is provided with a discharge outlet; the discharge hole of the solvent kettle is connected with the feed inlet of the mixing kettle through a first pipeline; a solvent volatilization outlet of the mixing kettle is connected with a feed inlet of the solvent recovery kettle through a second pipeline; the externally mounted of solvent cauldron has first heating device, the externally mounted of mixing cauldron has second heating device, still install first stirring rake in the mixing cauldron. Preferably, the first heating device and the second heating device are both heating coils.
As a preferred technical scheme, a second stirring paddle is arranged in the solvent kettle, and the second stirring paddle is used for enabling the lithium source in the solvent kettle to be uniformly dispersed in the organic solvent.
As a preferable technical scheme, a first locking valve is installed on the first pipeline, and a second locking valve is installed on the second pipeline. The opening or closing state of the first pipeline and the second pipeline can be respectively adjusted through the first locking valve and the second locking valve, and then the connection state among the solvent kettle, the mixing kettle and the solvent recovery kettle is adjusted. Further preferably, a spray head is installed at the end part of the second pipeline, which is positioned in the mixing kettle. Organic solvent with a lithium source dissolved can be sprayed into the mixing kettle in a small liquid drop shape through the spray head, so that materials in the mixing kettle can be fully contacted, and the materials can be mixed more uniformly.
As a preferred technical scheme, a condensing pipe is arranged on the outer wall of the solvent recovery kettle. By conveying cooling water into the condensation pipe, the temperature of the solvent recovery kettle can be accelerated to be reduced, and the cooling speed of the organic solvent is improved.
As a preferred technical scheme, the upper parts of the kettle walls of the solvent kettle and the mixing kettle are provided with air holes, the air holes are communicated with vacuum-pumping equipment or an inert gas pipeline, and the interior of the solvent kettle and the mixing kettle can be ensured to be in a vacuum state or an inert gas protection state through the air holes.
The invention also provides a method for carrying out liquid-phase pre-lithiation treatment on a silicon oxide negative electrode material, which is completed by using the device and comprises the following steps:
adding a lithium source and an organic solvent into a solvent kettle, heating by a first heating device to enable the temperature of the organic solvent to be higher than the melting point of the lithium source, and dispersing the lithium source in the organic solvent to obtain the organic solvent containing the lithium source;
adding a silicon monoxide negative electrode material into a mixing kettle, conveying an organic solvent containing a lithium source into the mixing kettle through a first pipeline, and uniformly mixing the lithium source and the silicon monoxide negative electrode material under the action of a first stirring paddle to obtain a mixed material;
heating by a second heating device to volatilize the organic solvent into the solvent recovery kettle for recovery, and discharging from a discharge hole at the bottom of the mixing kettle to obtain a mixed material;
and (3) placing the mixed material in a protective atmosphere environment for calcination treatment to complete the pre-lithiation treatment, thereby obtaining a final product.
As a preferred technical scheme, the organic solvent is a high-boiling point inert solvent, the boiling point of the organic solvent is higher than the melting point of the lithium source, and the organic solvent does not react with the lithium source chemically; the organic solvent is at least one of diformate (with a boiling point of 196 ℃), ethyl benzoate (with a boiling point of 212 ℃), 1, 3-trimethylcyclohexenone (with a boiling point of 213 ℃), N-methyl pyrrolidone (with a boiling point of 202 ℃) and diphenyl ether (with a boiling point of 259 ℃). The lithium source is a simple substance of metallic lithium, and is lithium foil, a lithium strip or a lithium ingot. Further, the temperature of the calcination treatment is 750-850 ℃.
Compared with the prior art, the invention has the beneficial effects that:
according to the device provided by the invention, firstly, a lithium source is dissolved in an organic solvent in a solvent kettle, then the mixing treatment of the lithium source and the silicon monoxide negative electrode material is completed in a mixing kettle, and finally, the organic solvent is recovered to an organic solvent recovery kettle, so that the recovery of the organic solvent is realized. The method can effectively solve the problem of potential safety hazard caused by volatilization of the organic solvent in the liquid phase method pretreatment process, can realize recycling of the organic solvent, can obviously reduce the production cost, and has good economic benefit.
The device can realize the pre-lithiation process of the silicon oxide negative electrode material under the liquid phase condition, and compared with a solid phase method and a gas phase method, the device has the advantages of lower treatment temperature, simple required equipment structure and capability of realizing industrial production.
The organic solvent selected by the invention is a high-boiling point inert solvent which does not react with lithium metal, so that the lithium metal keeps 0 valence and has strong reducibility, and the high-boiling point inert solvent only plays a role in heat conduction and lithium metal dispersion, so that the lithium metal is melted and dispersed in the solvent into fine particles and can fully react with the silicon monoxide negative electrode material; in addition, the proportion of the lithium metal and the organic solvent can be adjusted at will, the lithium doping amount can be adjusted according to the actual process requirement, and the operation is simple.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for liquid phase prelithiation of a silicon oxide negative electrode material according to the present invention;
fig. 2 is a first cycle charge and discharge curve diagram of CR2032 type button cell batteries made of the materials prepared in example 1 and comparative example 1;
reference numerals: 1-solvent kettle, 2-mixing kettle, 3-solvent recovery kettle, 4-first pipeline, 5-second pipeline, 6-first heating device, 7-second heating device, 8-first stirring paddle, 9-second stirring paddle, 10-first locking valve, 11-second locking valve, 12-spray head and 13-condensation pipe.
Detailed Description
The present invention will be further described with reference to the following examples and drawings so that those skilled in the art can better understand the present invention and can carry out the present invention, but the examples are not intended to limit the present invention.
It should be noted that "connect", "install", and the like in the present invention all mean that two components connected to each other are fixed together, generally by welding, screws, and the like, and those skilled in the art can understand the specific meaning of the above terms in the present invention according to specific situations. The terms "first" and "second" used herein do not denote any particular order or quantity, but rather are used to distinguish one element from another. It is to be understood that the terms "top," "bottom," "inner," "outer," and the like are used in an orientation or positional relationship indicated in the drawings for convenience in describing the present invention and for simplicity in description, and are not intended to indicate or imply that the referenced devices or elements must be in a particular orientation, constructed and operative in a particular orientation, and are not to be considered limiting of the present invention.
Referring to fig. 1, an apparatus for performing liquid-phase prelithiation treatment on a silica negative electrode material includes a solvent pot 1 for dissolving a lithium source in an organic solvent, a mixing pot 2 for mixing the silica negative electrode material and the lithium source, and a solvent recovery pot 3 for recovering the organic solvent; the top of the mixing kettle is provided with a feed inlet and a solvent volatilization outlet, and the bottom of the mixing kettle is provided with a discharge outlet; the discharge hole of the solvent kettle is connected with the feed inlet of the mixing kettle through a first pipeline 4; a solvent volatilization outlet of the mixing kettle is connected with a feed inlet of the solvent recovery kettle through a second pipeline 5; a first heating device 6 is arranged outside the solvent kettle 1; the second heating device 7 is arranged outside the mixing kettle 2, and the first stirring paddle 8 is arranged in the mixing kettle 2. Further, in order to uniformly disperse the lithium source in the solvent tank 1 in the organic solvent, a second stirring paddle 9 is installed in the solvent tank 1. In order to accelerate the condensation speed of the organic solvent recovered in the solvent recovery kettle, the condensation pipe 13 is installed on the outer wall of the solvent recovery kettle 3, and the temperature of the solvent recovery kettle 3 can be accelerated and reduced by conveying cooling water into the condensation pipe 13. Furthermore, the upper parts of the kettle walls of the solvent kettle 1 and the material mixing kettle 2 are provided with air holes (not shown in the figure), the air holes are communicated with vacuum pumping equipment or an inert gas pipeline, and the air holes can ensure that the interior of the solvent kettle and the interior of the material mixing kettle are in a vacuum state or an inert gas protection state; the first heating device 6 and the second heating device 7 are both heating coils.
In the preferred embodiment, a first lock valve 10 is mounted on the first pipe 4 and a second lock valve 11 is mounted on the second pipe 5. The opening or closing states of the first pipeline 4 and the second pipeline 5 can be respectively adjusted through the first locking valve 10 and the second locking valve 11, and then the connection states among the solvent kettle 1, the mixing kettle 2 and the solvent recovery kettle 3 are adjusted. Further preferred, tip department that second pipeline 5 is located the compounding cauldron installs shower nozzle 12, can make the organic solvent that dissolves the lithium source be little drop form and spray into the compounding cauldron through shower nozzle 12 in, make the interior material of compounding cauldron can fully contact to it is more even to make the material mix.
The device is used for carrying out liquid-phase pre-lithiation treatment on a silicon oxide negative electrode material, and the method is shown in the following embodiment:
example 1
2kg of SiO (D50 ═ 6um) is added into the mixing kettle 2, the first stirring paddle 8 is started, the second heating device 7 is started for heating, the temperature is kept at 190 ℃, the mixture is stored in vacuum, and the first locking valve 10 and the second locking valve 11 are kept closed. Adding diphenyl ether and 105g of lithium ingot into a solvent kettle 1, quickly vacuumizing, starting a first heating device 6 for heating, starting a second stirring paddle 9 for stirring, heating to 190 ℃, keeping the temperature for 3 hours, opening a first locking valve 10, dispersing lithium in a molten state in the diphenyl ether, then uniformly spraying the diphenyl ether dispersed with the lithium onto a SiO precursor in a mixing kettle 2 under the action of a spray head 12 through a first pipeline 4, and closing the first locking valve 10 after the materials in the solvent kettle 1 are completely sprayed. After the first stirring paddle 8 is continuously stirred for 3 hours at 190 ℃, the temperature in the mixing kettle is increased to 300 ℃, stirring is kept, the second locking valve 11 is opened, diphenyl ether is recovered to the solvent recovery kettle 3 through the second pipeline 5, and the condenser pipe 13 keeps cooling. And (3) taking out the lithium source from the mixing kettle 2 and uniformly mixing the lithium source with the silicon monoxide cathode material when the diphenyl ether is completely volatilized. And finally, putting the mixed material into a rotary furnace, and calcining for 5 hours at 800 ℃ under the protection of nitrogen to finish the pre-lithiation process.
Comparative example 1
Compared with example 1, comparative example 1 has the same process as example 1 except that only diphenyl ether and no lithium ingot are added to solvent tank 1.
The materials prepared in example 1 and comparative example 1 were used to prepare CR2032 button cells, and charge and discharge tests were performed, the test results of which are shown in table 1 and fig. 2.
Table 1 charge and discharge test data for CR2032 type button cell batteries made from the materials prepared in example 1 and comparative example 1
| DC-0.005V(mAh/g) | CC-1.5V(mAh/g) | 1st.C.E(1.5V，％) | |
| Example 1 | 1550.79 | 1326.57 | 85.54％ |
| Comparative example 1 | 2114.40 | 1628.07 | 77.00％ |
Remarking: in Table 1, DC-0.005 represents charging to 0.005V, CC-1.5V represents discharging to 1.5V, and 1stC.E represents first coulombic efficiency, and the calculation formula is as follows: 1st.C.E ═ CC/DC
As can be seen from table 1 and fig. 2, the initial coulombic efficiency of the CR2032 type button cell made of the material prepared in example 1 is 85.54%, and compared with 77.00% in comparative example 1, it is seen that the initial coulombic efficiency of the material is effectively improved by pre-lithium in example 1. The capacity of the battery made of the material after the pre-lithium treatment was slightly decreased as compared with comparative example 1, but in actual use, since the silicon negative electrode was used in combination with graphite, the total capacity was adjusted by adjusting the amount of addition. Compared with capacity loss, the effect of improving the first coulombic efficiency is larger.
It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. An apparatus for performing liquid phase prelithiation treatment on a silicon oxide negative electrode material, characterized in that: the lithium ion battery cathode material mixing device comprises a solvent kettle for dissolving a lithium source in an organic solvent, a mixing kettle for mixing a silicon monoxide cathode material and the lithium source, and a solvent recovery kettle for recovering the organic solvent; the top of the mixing kettle is provided with a feed inlet and a solvent volatilization outlet, and the bottom of the mixing kettle is provided with a discharge outlet; the discharge hole of the solvent kettle is connected with the feed inlet of the mixing kettle; and a solvent volatilization outlet of the mixing kettle is connected with a feed inlet of the solvent recovery kettle.
2. An apparatus for liquid phase prelithiation of a silicon oxide anode material according to claim 1, wherein: the solvent kettle is provided with a first heating device; the discharge hole of the solvent kettle is connected with the feed inlet of the mixing kettle through a first pipeline; a solvent volatilization outlet of the mixing kettle is connected with a feed inlet of the solvent recovery kettle through a second pipeline; the mixing kettle is provided with a second heating device and a first stirring paddle; and a second stirring paddle is arranged in the solvent kettle.
3. An apparatus for liquid phase prelithiation of a silicon oxide anode material according to claim 2, wherein: the first heating device and the second heating device are both heating coils.
4. An apparatus for liquid phase prelithiation of a silicon oxide anode material according to claim 2, wherein: and a first locking valve is arranged on the first pipeline, and a second locking valve is arranged on the second pipeline.
5. The apparatus of claim 4, wherein the apparatus is configured to perform liquid phase prelithiation of the silicon oxide negative electrode material, and wherein: and the end part of the second pipeline positioned in the mixing kettle is provided with a spray head.
6. The apparatus of claim 4, wherein the apparatus is configured to perform liquid phase prelithiation of the silicon oxide negative electrode material, and wherein: and a condensing pipe is arranged on the outer wall of the solvent recovery kettle.
7. An apparatus for liquid phase prelithiation of a silicon oxide anode material according to claim 1, wherein: and the upper parts of the kettle walls of the solvent kettle and the mixing kettle are provided with air holes, and the air holes are communicated with vacuum-pumping equipment or an inert gas pipeline.
8. A method for liquid phase prelithiation of a silicon oxide negative electrode material, characterized by: this is accomplished with the device according to any of claims 2 to 7, comprising the steps of:
adding a lithium source and an organic solvent into a solvent kettle, heating by a first heating device to enable the temperature of the organic solvent to be higher than the melting point of the lithium source, and dispersing the lithium source in the organic solvent to obtain the organic solvent containing the lithium source;
adding a silicon monoxide negative electrode material into a mixing kettle, conveying an organic solvent containing a lithium source into the mixing kettle through a first pipeline, and uniformly mixing the lithium source and the silicon monoxide negative electrode material under the action of a first stirring paddle to obtain a mixed material;
heating by a second heating device to volatilize the organic solvent into the solvent recovery kettle for recovery, and discharging from a discharge hole at the bottom of the mixing kettle to obtain a mixed material;
and (3) placing the mixed material in a protective atmosphere environment for calcination treatment to complete the pre-lithiation treatment, thereby obtaining a final product.
9. The method for liquid phase prelithiation of a silicon oxide anode material according to claim 8, wherein: the organic solvent is a high-boiling point inert solvent, the boiling point of the high-boiling point inert solvent is higher than the melting point of the lithium source, and the organic solvent does not react with the lithium source chemically; the organic solvent is at least one of diformate, ethyl benzoate, 1, 3-trimethylcyclohexenone, N-methyl pyrrolidone and diphenyl ether; the lithium source is a simple substance of metallic lithium, and is lithium foil, a lithium strip or a lithium ingot.
10. The method for liquid phase prelithiation of a silicon oxide anode material according to claim 8, wherein: the temperature of the calcination treatment is 750-850 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210439347.0A CN114824241A (en) | 2022-04-25 | 2022-04-25 | Device and method for carrying out liquid-phase pre-lithiation treatment on silicon monoxide negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210439347.0A CN114824241A (en) | 2022-04-25 | 2022-04-25 | Device and method for carrying out liquid-phase pre-lithiation treatment on silicon monoxide negative electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114824241A true CN114824241A (en) | 2022-07-29 |
Family
ID=82508101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210439347.0A Pending CN114824241A (en) | 2022-04-25 | 2022-04-25 | Device and method for carrying out liquid-phase pre-lithiation treatment on silicon monoxide negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114824241A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104766947A (en) * | 2014-01-03 | 2015-07-08 | 中国科学院物理研究所 | Preliminary metal metallization method and its application in battery material |
| US20170309950A1 (en) * | 2015-02-23 | 2017-10-26 | Sanyo Electric Co., Ltd. | NEGATIVE-ELECTRODE ACTIVE MATERIAL FOR NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY, NEGATIVE ELECTRODE FOR NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY, AND NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY (as amended) |
| CN206810243U (en) * | 2016-09-18 | 2017-12-29 | 深圳市傲川科技有限公司 | The surface treatment processing unit of conduction powder |
| CN110212152A (en) * | 2019-05-28 | 2019-09-06 | 合肥国轩高科动力能源有限公司 | Lithium ion battery pole piece roll-to-roll pre-lithiation method and device |
| CN111180660A (en) * | 2019-12-31 | 2020-05-19 | 兰溪致德新能源材料有限公司 | Liquid-phase lithium supplementing method for positive and negative electrode materials of lithium battery |
| CN111434609A (en) * | 2019-12-27 | 2020-07-21 | 蜂巢能源科技有限公司 | Pre-lithiated negative electrode active material, preparation method thereof, negative plate and lithium ion battery |
| CN112886000A (en) * | 2021-01-05 | 2021-06-01 | 昆山宝创新能源科技有限公司 | Pre-lithiated silica negative electrode material and preparation method and application thereof |
| CN113659123A (en) * | 2021-08-16 | 2021-11-16 | 四川金汇能新材料股份有限公司 | Negative electrode material, preparation method and equipment, and lithium ion battery |
-
2022
- 2022-04-25 CN CN202210439347.0A patent/CN114824241A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104766947A (en) * | 2014-01-03 | 2015-07-08 | 中国科学院物理研究所 | Preliminary metal metallization method and its application in battery material |
| US20170309950A1 (en) * | 2015-02-23 | 2017-10-26 | Sanyo Electric Co., Ltd. | NEGATIVE-ELECTRODE ACTIVE MATERIAL FOR NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY, NEGATIVE ELECTRODE FOR NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY, AND NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY (as amended) |
| CN206810243U (en) * | 2016-09-18 | 2017-12-29 | 深圳市傲川科技有限公司 | The surface treatment processing unit of conduction powder |
| CN110212152A (en) * | 2019-05-28 | 2019-09-06 | 合肥国轩高科动力能源有限公司 | Lithium ion battery pole piece roll-to-roll pre-lithiation method and device |
| CN111434609A (en) * | 2019-12-27 | 2020-07-21 | 蜂巢能源科技有限公司 | Pre-lithiated negative electrode active material, preparation method thereof, negative plate and lithium ion battery |
| CN111180660A (en) * | 2019-12-31 | 2020-05-19 | 兰溪致德新能源材料有限公司 | Liquid-phase lithium supplementing method for positive and negative electrode materials of lithium battery |
| CN112886000A (en) * | 2021-01-05 | 2021-06-01 | 昆山宝创新能源科技有限公司 | Pre-lithiated silica negative electrode material and preparation method and application thereof |
| CN113659123A (en) * | 2021-08-16 | 2021-11-16 | 四川金汇能新材料股份有限公司 | Negative electrode material, preparation method and equipment, and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 聂平;徐桂银;蒋江民;王江;付瑞瑞;方姗;窦辉;张校刚;: "预锂化技术及其在高比能硅负极中的应用" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106495161B (en) | A method of nano-silicon is prepared based on metal intervention metallothermic reduction | |
| CN110380030B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
| CN106186062B (en) | A kind of homogeneous hydro-thermal method prepares flower-shaped Cu2V2O7The method of material and the Cu of preparation2V2O7Material | |
| WO2022032747A1 (en) | Method for preparing sulfur-doped rese2/mxene composite material | |
| WO2024045723A1 (en) | Nanoscale sulfide solid electrolyte material and preparation method therefor | |
| WO2023024769A1 (en) | Method for preparing polyanion type sodium battery positive electrode material on the basis of organic acid dissolution method | |
| WO2020151094A1 (en) | Silicon oxide composite negative electrode material for lithium ion secondary battery and preparation method therefor | |
| CN104852039B (en) | Preparation method of cathode material for lithium ion battery | |
| WO2023179048A1 (en) | Fluorine-aluminum co-doped lithium cobalt oxide positive electrode material and preparation method therefor | |
| WO2023093142A1 (en) | Preparation method for high-voltage lithium cobalt oxide positive electrode material | |
| CN103972495A (en) | Preparation method of lithium ion battery positive pole material lithium nickelate manganate | |
| WO2023098169A1 (en) | Manganese-rich sodium-ion positive electrode material, preparation method therefor, and application thereof | |
| CN114634211B (en) | Preparation method and application of tin-based lithium cobalt oxide precursor | |
| CN111106314B (en) | High-temperature paste mixing method for positive electrode lead paste of lead-acid storage battery | |
| CN110571431B (en) | Li2FeSiO4@ mesoporous carbon lithium ion battery cathode material and preparation method thereof | |
| CN106450179A (en) | Preparation method of titanium-doping ferric fluoride positive electrode material | |
| CN109638275A (en) | A kind of selenium, the nickelic positive electrode of silicate codope and its preparation method and application | |
| CN114824241A (en) | Device and method for carrying out liquid-phase pre-lithiation treatment on silicon monoxide negative electrode material | |
| CN113241429A (en) | Preparation method of negative electrode active material | |
| CN105680007B (en) | A kind of doping type graphene modified lithium titanate composite negative pole material and preparation method thereof | |
| CN117049604A (en) | Ferrous polyanion type sodium ion battery positive electrode material and preparation method thereof | |
| CN114883551B (en) | Alumina-coated nano silicon and continuous preparation method and system thereof | |
| CN111115638A (en) | Preparation method of silicon-based negative electrode material | |
| CN110993915A (en) | SiO for lithium ion batteryxPreparation method of @ M @ CNTs composite anode material | |
| CN110627114A (en) | Modified lithium titanate negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220729 |
|
| RJ01 | Rejection of invention patent application after publication |