CN108807921B - Lithium battery negative electrode material and preparation method thereof - Google Patents
Lithium battery negative electrode material and preparation method thereof Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Abstract
The invention discloses a preparation method of a lithium battery cathode material. Firstly preparing a porous Fe-Sn-La-O-B-F primary product through hydrothermal reaction, then carrying out free radical polymerization on the surface of the porous Fe-Sn-La-O-B-F primary product to form polymer modified porous Fe-Sn-La-O-B-F, and finally calcining at the temperature of 550 ℃ in the nitrogen atmosphere to obtain Fe-Sn-La-O-B-F coated with a/F/B/Si/P co-doped carbon layer. The invention also discloses the lithium battery cathode material prepared by the preparation method and a lithium battery using the cathode material as a cathode material. The lithium battery cathode material disclosed by the invention is low in preparation cost, high in energy density, high in battery capacity, long in cycle life and good in conductivity.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium battery cathode material and a preparation method thereof.
Background
In recent years, the energy economy of fossil fuels has faced a serious challenge, becoming a major factor that has restricted social progress and economic development. Under the situation, lithium ion batteries, which are clean and environmentally friendly and have high energy efficiency, have attracted attention in the industry and become an indispensable part of people's lives with the potential of being too fast to cover the ears. The lithium battery has the advantages of high energy density, high voltage, long cycle life, low self-discharge rate, no memory effect, stable discharge voltage, quick charge and discharge, environmental protection and the like, and is widely applied to the field of electronic products such as mobile phones, portable computers, cameras, video cameras and the like.
The negative electrode material of lithium battery is one of the important elements of lithium battery, and the performance of the negative electrode material directly affects the battery capacity and the cycle service life of the lithium battery. Lithium ion battery negative electrode materials reported in the prior art mainly include: graphitized carbon materials and transition metal oxide based materials. The graphitized carbon material has some disadvantages that, when lithium ions are intercalated, a part of the solvent is also intercalated, and the structure is easily damaged. The transition metal oxide material has larger volume expansion and contraction change in the process of lithium ion insertion and extraction, so that electrode material pulverization is caused, and electric contact with a current collector is lost, and the cycle performance and application of the material are greatly influenced.
Therefore, it is imperative to find a more efficient method for preparing a negative electrode material for a lithium battery, which is low in price, high in energy density, high in battery capacity, and long in cycle life.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a lithium battery cathode material which is low in price, high in energy density, high in battery capacity, long in cycle life and good in conductivity, and a preparation method thereof. The invention is realized by the following scheme:
a preparation method of a lithium battery negative electrode material comprises the following steps:
adding ferric trichloride, stannic chloride, titanium tetrachloride, lanthanum chloride and sodium tetrafluoroborate into a beaker of ethylene glycol, stirring for 1-2 hours, slowly adding sodium acetate, then stirring vigorously for 2-3 hours, transferring the solution into a hydrothermal reaction kettle with a polyfluoroethylene lining, and reacting for 20-25 hours at 180-200 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally separating out precipitate, washing, performing suction filtration, and finally drying the obtained sample at the temperature of 110-120 ℃ for 18-25 hours to obtain a product, namely porous Fe-Sn-La-O-B-F;
II, adding the porous Fe-Sn-La-O-B-F, trimethylvinylsilane, 4,5, 5-tetramethyl-2- (4-trifluorovinyloxy-phenyl) - [1,3,2] dioxaborane, vinylcarbazole, dimethyl vinylphosphate and an initiator which are prepared in the step I into a high-boiling-point solvent, stirring and reacting for 6-8 hours at the temperature of 60-70 ℃, and then centrifugally separating out a precipitate, washing and carrying out suction filtration to obtain surface-modified porous Fe-Sn-La-O-B-F; and then drying the mixture in a vacuum drying oven at the temperature of 80-90 ℃ for 20-24 hours, and finally calcining the dried mixture at the temperature of 550 ℃ under the nitrogen atmosphere to obtain the Fe-Sn-La-O-B-F coated by the/F/B/Si/P co-doped carbon layer.
Preferably, in the step I, the mass ratio of the ferric trichloride to the stannic chloride to the titanium tetrachloride to the lanthanum chloride to the sodium tetrafluoroborate to the glycol to the sodium acetate is 1:1:1:0.1:0.2 (30-50: 10).
Preferably, the mass ratio of the porous Fe-Sn-La-O-B-F, the trimethylvinylsilane, the 4,4,5, 5-tetramethyl-2- (4-trifluorovinyloxy-phenyl) - [1,3,2] dioxaborane, the vinylcarbazole, the vinyl dimethyl phosphate, the initiator and the high-boiling-point solvent in the step II is (12-14) to 0.2 to 0.3 to 0.5 to 0.02 to (40-50).
Preferably, the initiator is selected from one or more of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the high boiling point solvent is selected from one or more of N-methyl pyrrolidone, N-dimethylformamide and dimethyl sulfoxide.
A lithium battery negative electrode material is prepared by the preparation method of the lithium battery negative electrode material.
A lithium battery adopts the negative electrode material of the lithium battery as the negative electrode material.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
1) the preparation method of the lithium battery cathode material provided by the invention has the advantages of simple and easy operation process, and no harsh requirements on equipment and reaction conditions, and is suitable for large-scale industrial production.
2) The lithium battery cathode material provided by the invention overcomes the technical problems that partial solvent is also embedded when lithium ions are embedded and the structure is easy to damage in the traditional graphitized carbon material in the prior art, and also overcomes the technical problems that the traditional transition metal oxide material has larger volume expansion and contraction change in the process of lithium ion embedding and extracting, so that the electrode material is pulverized and further loses electric contact with a current collector, and the cycle performance and the application of the material are greatly influenced.
3) The lithium battery cathode material provided by the invention adopts a multi-element metal oxide porous structure, provides mechanical supporting force for the volume expansion of the lithium battery cathode material, can effectively keep the structural integrity of the material in the process of lithium ion insertion and extraction, and can ensure stable electrochemical performance through the synergistic effect of in-vivo doping B/F.
4) According to the lithium battery cathode material provided by the invention, the N/F/Si/P/B co-doped carbon layer is coated on the surface of the porous multi-element metal oxide, so that the specific capacity and the conductivity of the material can be improved, the structure of the material with the porous structure can be stabilized, and the electrode material pulverization caused by large volume expansion and contraction change in the process of lithium ion insertion and extraction can be avoided.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
The raw materials described in the following examples of the present invention are from Shanghai spring Xin import & export trade company, Inc.
Example 1
A preparation method of a lithium battery negative electrode material comprises the following steps:
i, adding 10g of ferric trichloride, 10g of stannic chloride, 10g of titanium tetrachloride, 1g of lanthanum chloride and 2g of sodium tetrafluoroborate into a beaker containing 300g of ethylene glycol, stirring for 1 hour, slowly adding 100g of sodium acetate, stirring vigorously for 2 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 20 hours at 180 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally separating out precipitate, washing, performing suction filtration, and finally drying the obtained sample at 110 ℃ for 18 hours to obtain a product, namely porous Fe-Sn-La-O-B-F;
II, adding 0.2g of trimethylvinylsilane, 0.3g of 4,4,5, 5-tetramethyl-2- (4-trifluorovinyloxy-phenyl) - [1,3,2] dioxaborane, 0.5g of vinylcarbazole, 0.5g of vinyl dimethyl phosphate and 0.02g of azobisisobutyronitrile into 40g of N-methylpyrrolidone, stirring and reacting for 6 hours at 60 ℃, and then centrifugally separating out precipitate, washing and carrying out suction filtration to obtain surface-modified porous Fe-Sn-La-O-B-F; and then drying the mixture in a vacuum drying oven at the temperature of 80 ℃ for 20 hours, and finally calcining the dried mixture at the temperature of 450 ℃ in a nitrogen atmosphere to obtain the Fe-Sn-La-O-B-F coated by the/F/B/Si/P co-doped carbon layer.
A lithium battery negative electrode material is prepared by the preparation method of the lithium battery negative electrode material.
A lithium battery adopts the negative electrode material of the lithium battery as the negative electrode material.
The lithium battery button cell is prepared from the lithium battery cathode material prepared by the method: uniformly mixing the prepared lithium battery negative electrode material, Super P and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, then dripping N-methylpyrrolidone solution (NMP) into the mixture, uniformly stirring the mixture to form viscous pasty viscous liquid, then uniformly coating the viscous liquid on copper foil through a coating machine, drying the coated copper foil in a 100 ℃ vacuum drying oven for 24 hours (removing NMP solvent and a small amount of residual moisture), cooling the dried copper foil to room temperature, taking the cooled copper foil out, using a slicing machine to prepare a wafer with the diameter of 14cm from the copper foil, compacting the wafer to serve as a negative electrode plate, and finally assembling the wafer-type battery 2016 in a glove box filled with argon. And (3) charging and discharging the assembled button cell for 100 circles on a LAND cell test system at a multiplying power of 0.1C, wherein the voltage range is 0.05-3.0V, and the measured specific discharge capacity is 940 mAh/g.
Example 2
A preparation method of a lithium battery negative electrode material comprises the following steps:
i, adding 10g of ferric trichloride, 10g of stannic chloride, 10g of titanium tetrachloride, 1g of lanthanum chloride and 2g of sodium tetrafluoroborate into a beaker containing 350g of ethylene glycol, stirring for 1.2 hours, slowly adding 100g of sodium acetate, stirring vigorously for 2.3 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 22 hours at 185 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally separating out precipitate, washing, performing suction filtration, and finally drying the obtained sample at 112 ℃ for 19 hours to obtain a product, namely porous Fe-Sn-La-O-B-F;
II, adding 0.2g of trimethylvinylsilane, 0.3g of 4,4,5, 5-tetramethyl-2- (4-trifluorovinyloxy-phenyl) - [1,3,2] dioxaborane, 0.5g of vinylcarbazole, 0.5g of dimethyl vinylphosphate and 0.02g of azobisisoheptonitrile into 43g of N, N-dimethylformamide, stirring and reacting at 63 ℃ for 6.5 hours, and then centrifugally separating out precipitate, washing and carrying out suction filtration to obtain surface-modified porous Fe-Sn-La-O-B-F; and then drying the mixture in a vacuum drying oven at 83 ℃ for 22 hours, and finally calcining the dried mixture at 480 ℃ in a nitrogen atmosphere to obtain the Fe-Sn-La-O-B-F coated by the/F/B/Si/P co-doped carbon layer.
A lithium battery negative electrode material is prepared by the preparation method of the lithium battery negative electrode material.
A lithium battery adopts the negative electrode material of the lithium battery as the negative electrode material.
The prepared porous titanium dioxide material for the lithium battery negative electrode is prepared into a negative electrode plate according to the method in the embodiment 1, the negative electrode plate is manufactured into a button cell, the button cell is charged and discharged for 100 circles on a LAND cell test system at 0.1C multiplying power, and the specific discharge capacity is 937 mAh/g.
Example 3
A preparation method of a lithium battery negative electrode material comprises the following steps:
i, adding 10g of ferric trichloride, 10g of stannic chloride, 10g of titanium tetrachloride, 1g of lanthanum chloride and 2g of sodium tetrafluoroborate into a beaker containing 400g of ethylene glycol, stirring for 1.5 hours, slowly adding 100g of sodium acetate, stirring vigorously for 2.5 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 23 hours at 190 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally separating out precipitate, washing, performing suction filtration, and finally drying the obtained sample at 115 ℃ for 21 hours to obtain a product, namely porous Fe-Sn-La-O-B-F;
II, adding 0.3g of trimethyl vinyl silane, 0.2g of 4,4,5, 5-tetramethyl-2- (4-trifluorovinyloxy-phenyl) - [1,3,2] dioxaborane, 0.5g of vinyl carbazole, 0.5g of vinyl dimethyl phosphate and 0.02g of azobisisobutyronitrile into 46g of dimethyl sulfoxide, stirring and reacting for 7 hours at 66 ℃, and then centrifugally separating out a precipitate, washing and carrying out suction filtration to obtain surface-modified porous Fe-Sn-La-O-B-F; and then drying the mixture in a vacuum drying oven at 86 ℃ for 23 hours, and finally calcining the dried mixture at 500 ℃ in a nitrogen atmosphere to obtain the Fe-Sn-La-O-B-F coated by the/F/B/Si/P co-doped carbon layer.
A lithium battery negative electrode material is prepared by the preparation method of the lithium battery negative electrode material.
A lithium battery adopts the negative electrode material of the lithium battery as the negative electrode material.
The prepared porous titanium dioxide material for the lithium battery negative electrode is prepared into a negative electrode plate according to the method in the embodiment 1, the negative electrode plate is manufactured into a button cell, the button cell is charged and discharged for 100 circles on a LAND cell test system at 0.1C multiplying power, and the specific discharge capacity is 934 mAh/g.
Example 4
A preparation method of a lithium battery negative electrode material comprises the following steps:
i, adding 10g of ferric trichloride, 10g of stannic chloride, 10g of titanium tetrachloride, 1g of lanthanum chloride and 2g of sodium tetrafluoroborate into a beaker containing 450g of ethylene glycol, stirring for 1.8 hours, slowly adding 100g of sodium acetate, stirring vigorously for 2.8 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 24 hours at 195 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally separating out precipitate, washing, performing suction filtration, and finally drying the obtained sample at 118 ℃ for 24 hours to obtain a product, namely porous Fe-Sn-La-O-B-F;
II, adding 0.2g of trimethylvinylsilane, 0.3g of 4,4,5, 5-tetramethyl-2- (4-trifluorovinyloxy-phenyl) - [1,3,2] dioxaborane, 0.5g of vinylcarbazole, 0.5g of vinyl dimethyl phosphate and 0.02g of initiator into 48g of high-boiling-point solvent, stirring and reacting for 7.5 hours at 68 ℃, and then centrifugally separating out a precipitate, washing and carrying out suction filtration to obtain surface-modified porous Fe-Sn-La-O-B-F; then drying in a vacuum drying oven at 88 ℃ for 23 hours, and finally calcining at 530 ℃ in a nitrogen atmosphere to obtain Fe-Sn-La-O-B-F coated by a/F/B/Si/P co-doped carbon layer; the initiator is a mixture formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5; the high boiling point solvent is a mixture formed by mixing N-methyl pyrrolidone, N-dimethylformamide and dimethyl sulfoxide according to the mass ratio of 1:2: 3.
A lithium battery negative electrode material is prepared by the preparation method of the lithium battery negative electrode material.
A lithium battery adopts the negative electrode material of the lithium battery as the negative electrode material.
The prepared porous titanium dioxide material for the lithium battery negative electrode is prepared into a negative electrode plate according to the method in the embodiment 1, the negative electrode plate is manufactured into a button cell, the button cell is charged and discharged for 100 circles on a LAND cell test system at 0.1C multiplying power, and the specific discharge capacity is 942 mAh/g.
Example 5
A preparation method of a lithium battery negative electrode material comprises the following steps:
i, adding 10g of ferric trichloride, 10g of stannic chloride, 10g of titanium tetrachloride, 1g of lanthanum chloride and 2g of sodium tetrafluoroborate into a beaker containing 500g of ethylene glycol, stirring for 2 hours, slowly adding 100g of sodium acetate, stirring vigorously for 3 hours, transferring the solution into a hydrothermal reaction kettle with a polyvinyl fluoride lining, and reacting for 25 hours at 200 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally separating out precipitate, washing, performing suction filtration, and finally drying the obtained sample at 120 ℃ for 25 hours to obtain a product, namely porous Fe-Sn-La-O-B-F;
II, adding 0.2g of trimethylvinylsilane, 0.3g of 4,4,5, 5-tetramethyl-2- (4-trifluorovinyloxy-phenyl) - [1,3,2] dioxaborane, 0.5g of vinylcarbazole, 0.5g of vinyl dimethyl phosphate and 0.02g of azobisisoheptonitrile into 50g of N, N-dimethylformamide, stirring and reacting for 8 hours at 70 ℃, and then centrifugally separating out precipitate, washing and carrying out suction filtration to obtain surface-modified porous Fe-Sn-La-O-B-F; and then drying the mixture in a vacuum drying oven at 90 ℃ for 24 hours, and finally calcining the dried mixture at 550 ℃ in a nitrogen atmosphere to obtain the Fe-Sn-La-O-B-F coated by the/F/B/Si/P co-doped carbon layer.
A lithium battery negative electrode material is prepared by the preparation method of the lithium battery negative electrode material.
A lithium battery adopts the negative electrode material of the lithium battery as the negative electrode material.
The prepared porous titanium dioxide material for the lithium battery negative electrode is prepared into a negative electrode plate according to the method in the embodiment 1, the negative electrode plate is manufactured into a button cell, the button cell is charged and discharged for 100 circles on a LAND cell test system at 0.1C multiplying power, and the specific discharge capacity is 938 mAh/g.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (2)
1. The preparation method of the lithium battery negative electrode material is characterized by comprising the following steps of:
adding ferric trichloride, stannic chloride, titanium tetrachloride, lanthanum chloride and sodium tetrafluoroborate into a beaker of ethylene glycol, stirring for 1-2 hours, slowly adding sodium acetate, then violently stirring for 2-3 hours, transferring the solution into a hydrothermal reaction kettle with a polyfluoroethylene lining, and reacting for 20-25 hours at 180 ℃ and 200 ℃; after the reaction is finished, cooling the reaction kettle to room temperature, centrifugally separating out precipitate, washing, performing suction filtration, and finally drying the obtained sample at the temperature of 110-120 ℃ for 18-25 hours to obtain a product, namely porous Fe-Sn-La-O-B-F; the mass ratio of the ferric trichloride to the stannic chloride to the titanium tetrachloride to the lanthanum chloride to the sodium tetrafluoroborate to the ethylene glycol to the sodium acetate is 1:1:1:0.1:0.2 (30-50: 10);
II, adding the porous Fe-Sn-La-O-B-F, trimethylvinylsilane, 4,5, 5-tetramethyl-2- (4-trifluorovinyloxy-phenyl) - [1,3,2] dioxaborane, vinylcarbazole, dimethyl vinylphosphate and an initiator which are prepared in the step I into a high-boiling-point solvent, stirring and reacting for 6-8 hours at the temperature of 60-70 ℃, and then centrifugally separating out a precipitate, washing and carrying out suction filtration to obtain surface-modified porous Fe-Sn-La-O-B-F; then drying the mixture in a vacuum drying oven at the temperature of 80-90 ℃ for 20-24 hours, and finally calcining the mixture at the temperature of 550 ℃ under the nitrogen atmosphere to obtain the Fe-Sn-La-O-B-F coated by the N/F/B/Si/P co-doped carbon layer; the mass ratio of the porous Fe-Sn-La-O-B-F, the trimethylvinylsilane, the 4,4,5, 5-tetramethyl-2- (4-trifluorovinyloxy-phenyl) - [1,3,2] dioxaborane, the vinylcarbazole, the vinyl dimethyl phosphate, the initiator and the high-boiling-point solvent is (12-14):0.2:0.3:0.5:0.5:0.02 (40-50); the high boiling point solvent is selected from one or more of N-methyl pyrrolidone, N-dimethyl formamide and dimethyl sulfoxide.
2. The method for preparing the negative electrode material for the lithium battery as claimed in claim 1, wherein the initiator is one or more selected from azobisisobutyronitrile and azobisisoheptonitrile.
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| CN201810633302.0A CN108807921B (en) | 2018-06-20 | 2018-06-20 | Lithium battery negative electrode material and preparation method thereof |
| CN202010658960.2A CN111916695A (en) | 2018-06-20 | 2018-06-20 | High-energy-density lithium battery |
| CN202010658966.XA CN111916696A (en) | 2018-06-20 | 2018-06-20 | High-capacity lithium battery negative electrode material |
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| CN108807921A (en) | 2018-11-13 |
| CN111916695A (en) | 2020-11-10 |
| CN111916696A (en) | 2020-11-10 |
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