CN109873125B - SnPO4Application in lithium ion battery cathode - Google Patents
SnPO4Application in lithium ion battery cathode Download PDFInfo
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- CN109873125B CN109873125B CN201711248795.8A CN201711248795A CN109873125B CN 109873125 B CN109873125 B CN 109873125B CN 201711248795 A CN201711248795 A CN 201711248795A CN 109873125 B CN109873125 B CN 109873125B
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Abstract
The invention relates to a SnPO4The lithium ion battery cathode is applied to the lithium ion battery cathode. The SnPO4The compound is used as an active material to be applied to a lithium ion battery cathode. The lithium ion battery cathode material has the advantages of low average working voltage, high specific capacity, good charge and discharge performance of the lithium ion battery, excellent cycle performance and capability of being used as a lithium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a negative electrode material for a lithium ion battery.
Background
With the increasing severity of energy problems, the increasing scarcity of non-renewable resources, and the increasing awareness of people on the importance of environmental protection, the social demand for new energy is increasing, and stored energy plays an increasingly important role in energy systems. The lithium ion battery has the advantages of high working voltage, good rate performance, long cycle life, high energy density, small self-discharge, no memory effect and the like. Lithium ion batteries have been widely used in small portable electronic devices, and are also the first choice of power batteries, and will occupy a large share in the electrochemical energy storage market in the future, so the research on lithium ion batteries has been one of the hot spots in the research on energy storage technology.
Is currently applied toThe negative electrode material of the lithium ion battery mainly comprises carbon materials such as graphite, mesocarbon microbeads, graphene and the like, lithium titanate and the like. However, these materials still suffer from a number of problems: the specific capacity is low, the mass energy density and the volume energy density are low, and the like, and the materials can not meet the development requirement of the next generation of high specific energy lithium ion battery. The metal oxide-based novel negative electrode material is considered as a negative electrode material for next-generation high-specific-energy lithium ion batteries due to its high theoretical specific capacity and low cost. The alloyed negative electrode is a novel negative electrode material, and has high theoretical specific capacity through multi-electron reaction with lithium in the discharge process. Sn can generate alloying reaction with Li, and the compound can be used as a lithium ion battery cathode material and has high theoretical specific capacity. Containing PO4 3-The polyanionic materials of (a) have high structural stability because of their better cyclic stability. SnPO4The compound has high theoretical specific capacity, and can improve the conductivity of the material by being compounded with a carbon material, thereby improving the electrochemical performance of the electrode material.
Disclosure of Invention
In view of the above-mentioned technical problems, the present invention aims to provide an SnPO4the/C is used as a negative electrode material in the lithium ion battery;
the specific technical scheme is as follows:
SnPO4Application of/C in negative electrode of lithium ion battery, and SnPO4the/C compound is used as an active material to be applied to a negative electrode of a lithium ion battery.
The negative active material of the lithium ion battery is SnPO4And C, material.
The invention provides SnPO4The negative electrode material of the/C lithium ion battery.
SnPO preparation by hydrothermal method4The negative electrode material of the/C lithium ion battery comprises the following steps:
1) preparing materials: SnPO4Adding the organic carbon source compound and 100-200mL deionized water according to the molar ratio of 1 (0.5-1) for ultrasonic dispersion for 10-30 minutes to form uniform dispersion liquid;
2) transferring the dispersion liquid into a hydrothermal reaction kettle for pretreatment;
the pretreatment is to heat the hydrothermal reaction kettle from room temperature to 160-200 ℃ for more than 12-24 hours, then cool the hydrothermal reaction kettle to room temperature, centrifugally separate the precipitate, wash and dry the precipitate to obtain a pretreated material;
3) controlling various parameters to synthesize the material: pretreating the material obtained in the step 2); raising the temperature to 450-750 ℃ at the speed of 1-10 ℃/min; preserving the heat for 3-5 hours under the argon atmosphere; after the reaction is fully carried out, the temperature is reduced to the room temperature at the speed of 1-50 ℃/h to obtain SnPO4a/C material;
the organic carbon source compound is one or more than two of glucose, sucrose, citric acid and malic acid;
SnPO preparation by sol-gel method4The negative electrode material of the/C lithium ion battery comprises the following steps:
1) preparing materials: SnPO4Adding the organic carbon source compound and the organic carbon source compound into 40-80mL deionized water according to the molar ratio of 1 (0.5-1) to perform ultrasonic dispersion for 10-30 minutes to form uniform dispersion liquid; heating the dispersion liquid to 50-100 ℃, and continuously stirring until sol is formed;
2) transferring the sol to a drying oven at the temperature of 100-200 ℃, drying the sol to gel, grinding the gel into powder and then carrying out pretreatment;
the pretreatment is to heat the mixture from room temperature to 200-500 ℃ for more than 2-10 hours in an argon atmosphere and then cool the mixture to room temperature;
3) controlling various parameters to synthesize the material: pretreating the material obtained in the step 2); raising the temperature to 450-750 ℃ at the speed of 1-10 ℃/min; preserving the heat for 3-5 hours under the argon atmosphere; after the reaction is fully carried out, the temperature is reduced to the room temperature at the speed of 1-50 ℃/h to obtain SnPO4a/C material;
the organic carbon source compound is one or more than two of glucose, sucrose, citric acid and malic acid;
a few typical available SnPO's are listed below4The chemical reaction formula of the/C complex is as follows:
(1)SnCl4+NH3·H2O＝Sn(OH)4+NH4Cl
(2)Sn(OH)4+H3PO4+1/2C＝SnPO4+4H2O+1/2CO↑+1/2H2O
the invention has the advantages that: obtained SnPO4the/C negative electrode material presents black powder (fig. 1), has better crystallinity (fig. 2), has higher specific capacity (fig. 4), rate capability (fig. 5) and cycling stability. SnPO4the/C lithium ion battery cathode material has the working voltage of about 0.4V, has higher specific capacity of 1215mAh/g, is higher one of the existing known lithium ion battery cathode materials, and can still keep the specific capacity of more than 95 percent after 200 cycles.
Drawings
FIG. 1 is a SnPO of the present invention4SEM pictures of/C lithium ion battery cathode materials.
FIG. 2 shows an SnPO of the present invention4The polycrystalline powder X-ray diffraction pattern of (a).
FIG. 3 shows an SnPO of the present invention4Crystal structure of (2).
FIG. 4 shows an SnPO of the present invention4The charge-discharge curve of the negative electrode material of the/C lithium ion battery is 1C multiplying power and 0.01-3.0V.
FIG. 5 shows an SnPO of the present invention4And (3) a cycle performance curve of the negative electrode material of the/C lithium ion battery under the multiplying power of 1C.
Detailed Description
Example 1 SnPO4Hydrothermal preparation of/C cathode material
5.26g of SnCl4Dissolving in 100g deionized water, stirring to obtain a uniform solution, adding 3.46g phosphoric acid (85%), mixing, and stirring for 30 minutes to obtain a clear solution; adding 0.1g of hexadecyl trimethyl ammonium bromide until the hexadecyl trimethyl ammonium bromide is dissolved, adding 25 mass percent of ammonia water until the pH value is 2.7, and filtering and separating a precipitate; the precursor obtained by precipitation is washed and dried for 5 hours at 85 ℃. Heating the dried pretreated ingredients for 2 days at 65 ℃ under argon atmosphere; then raising the temperature from room temperature to 240 ℃ at the speed of 5 ℃/min, and preserving the temperature for 3 hours; after the reaction is fully carried out, the temperature is reduced to the room temperature at the speed of 20 ℃/h to obtain SnPO4A material; 0.5g of SnPO4Adding 0.6g of glucose into 100mL of deionized water, and performing ultrasonic dispersion for 30 minutes to form a uniform dispersion liquid; transferring the dispersion to hydrothermal reactionHeating the mixture in a kettle from room temperature to 180 ℃ for 12 hours, cooling the mixture to room temperature, centrifugally separating the precipitate, washing and drying the precipitate to obtain a precursor; the precursor is raised to 500 ℃ at the speed of 5 ℃/min; preserving the heat for 3 hours under the argon atmosphere; after the reaction is fully carried out, the temperature is reduced to the room temperature at the speed of 20 ℃/h to obtain SnPO4a/C material;
as shown in fig. 1, it is a black powder; the X-ray diffraction spectrum is shown in figure 2, and the crystal structure diagram is shown in figure 3.
Example 2 SnPO4Sol-gel preparation of negative electrode materials
5.26g of SnCl4Dissolving in 100g deionized water, stirring to obtain a uniform solution, adding 3.46g phosphoric acid (85%), mixing, and stirring for 30 minutes to obtain a clear solution; adding 0.1g of hexadecyl trimethyl ammonium bromide until the hexadecyl trimethyl ammonium bromide is dissolved, adding 25 mass percent of ammonia water until the pH value is 2.7, and filtering and separating a precipitate; the precursor obtained by precipitation is washed and dried for 5 hours at 85 ℃. Heating the dried pretreated ingredients for 2 days at 65 ℃ under argon atmosphere; then raising the temperature from room temperature to 240 ℃ at the speed of 5 ℃/min, and preserving the temperature for 3 hours; after the reaction is fully carried out, the temperature is reduced to the room temperature at the speed of 1-50 ℃/h to obtain SnPO4A material; 0.5g of SnPO4Adding 0.8g of cane sugar into 80mL of deionized water, and performing ultrasonic dispersion for 30 minutes to form uniform dispersion liquid; heating the dispersion liquid to 90 ℃, and continuously stirring until sol is formed; transferring the sol into a drying oven at 120 ℃, drying to obtain gel, grinding the gel into powder, heating to 350 ℃ from room temperature under argon atmosphere for 3 hours, and cooling to room temperature; then the pretreated material is raised to 500 ℃ at the speed of 5 ℃/min; preserving the heat for 3 hours under the argon atmosphere; after the reaction is fully carried out, the temperature is reduced to the room temperature at the speed of 20 ℃/h to obtain SnPO4a/C material;
the materials obtained in examples 1 and 2 were dissolved in an appropriate amount of N-methylpyrrolidone in a mass ratio of 8:1:1 of active material, conductive carbon black and binder, mixed uniformly, coated into an electrode film having a thickness of 0.15mm using a wet film maker, vacuum-dried, cut into electrode pieces having a diameter of 12mm using a slicer, weighed and calculated for the mass of the active material. Meanwhile, 1mo of lithium sheet is used as a negative electrode, Celgard 2500 is used as a diaphragmL/L LiPF6The EC + DMC (volume ratio 1:1) solution of (A) was used as an electrolyte and a coin cell was placed in an argon-filled glove box. The assembled cells were then subjected to electrochemical testing, each at 0.01-3.0V constant current. The test results are shown in FIGS. 4 and 5, and it can be seen that SnPO4Has higher specific discharge capacity in the lithium ion battery, which reaches 1215mAhg-1And has good cycle performance, 1A g-1972.3mAhg still remained after 200 cycles of current density-1The specific capacity of (A).
The lithium ion battery has better charge and discharge performance and good cycle stability.
Claims (3)
1. SnPO4The application of the SnPO in the negative electrode of the lithium ion battery is characterized in that4The compound is used as an active material to be applied to a lithium ion battery cathode; the lithium ion battery cathode material is SnPO4SnPO composite material with carbon4C, wherein the mass content of C is 10-50%; the mass ratio of the negative electrode of the lithium ion battery is SnPO4Conductive carbon =99:1 to 50: 50; SnPO4The preparation method adopts a precipitation method and comprises the following steps:
1) preparing materials: mixing a Sn-containing compound and a P-containing compound according to the molar ratio of Sn to P (1-1.2:2), mixing with a surfactant, and carrying out pretreatment;
the pretreatment comprises the steps of uniformly mixing the prepared raw materials, adding the uniformly mixed raw materials into deionized water to obtain a uniform solution, adding a precipitator into the uniform solution, stirring the solution, and performing suction filtration and separation to obtain a pretreated ingredient;
2) controlling various parameters to synthesize the material: washing the pretreated ingredients, and drying at 80-100 ℃ for 3-5 hours; heating the dried pretreated ingredients for 24-48 hours at 60-80 ℃ under argon atmosphere, preferably at 75-80 ℃ in argon for 24-36 hours; raising the temperature from room temperature to 200 ℃ and 400 ℃ at the speed of 1-10 ℃/min, and preserving the heat for 2-4 hours; after the reaction is fully carried out, the temperature is reduced to the room temperature at the speed of 1-50 ℃/h to obtain SnPO4A material;
the Sn-containing compound is one or more than two of tetravalent Sn oxide, tetravalent Sn hydrochloride, tetravalent Sn sulfate and divalent Sn hydrochloride;
the compound containing P is one or two of phosphoric acid, ammonium dihydrogen phosphate, potassium phosphate and sodium phosphate;
the surfactant is one or two of cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide;
the precipitator is NH3·H2One or more of O, NaOH and KOH.
2. Use according to claim 1, characterised in that SnPO is prepared by hydrothermal method4The negative electrode material of the/C lithium ion battery comprises the following steps:
1) preparing materials: SnPO4Adding the organic carbon source compound and 100-200mL deionized water according to the molar ratio of 1 (0.5-1) for ultrasonic dispersion for 10-30 minutes to form uniform dispersion liquid;
2) transferring the dispersion liquid into a hydrothermal reaction kettle for pretreatment;
the pretreatment is to heat the hydrothermal reaction kettle from room temperature to 160-200 ℃ for more than 12-24 hours, then cool the hydrothermal reaction kettle to room temperature, centrifugally separate the precipitate, wash and dry the precipitate to obtain a pretreated material;
3) controlling various parameters to synthesize the material: pretreating the material obtained in the step 2); raising the temperature from room temperature to 450-750 ℃ at the speed of 1-10 ℃/min; preserving the heat for 3-5 hours under the argon atmosphere; after the reaction is fully carried out, the temperature is reduced to the room temperature at the speed of 1-50 ℃/h to obtain SnPO4a/C material;
the organic carbon source compound is one or more than two of glucose, sucrose, citric acid and malic acid.
3. Use according to claim 1, characterized in that the SnPO is prepared by a sol-gel process4The negative electrode material of the/C lithium ion battery comprises the following steps:
1) preparing materials: SnPO4Adding the mixture and an organic carbon source compound into deionized water according to the molar ratio of 1 (0.5-1) for ultrasonic dispersion for 10-30 minutes to form uniformA dispersion liquid; heating the dispersion liquid to 50-100 ℃, and continuously stirring until sol is formed;
2) transferring the separated sol to a drying oven at the temperature of 100-200 ℃, drying the separated sol to gel, grinding the gel into powder and then carrying out pretreatment;
the pretreatment is to heat the mixture from room temperature to 200-500 ℃ for more than 2-10 hours in an argon atmosphere and then cool the mixture to room temperature;
3) controlling various parameters to synthesize the material: pretreating the material obtained in the step 2); raising the temperature from room temperature to 450-750 ℃ at the speed of 1-10 ℃/min; preserving the heat for 3-5 hours under the argon atmosphere; after the reaction is fully carried out, the temperature is reduced to the room temperature at the speed of 1-50 ℃/h to obtain SnPO4a/C material;
the organic carbon source compound is one or more than two of glucose, sucrose, citric acid and malic acid.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101483234A (en) * | 2008-01-08 | 2009-07-15 | 三星Sdi株式会社 | Electrode assembly and lithium secondary battery having the same |
| JP2009249194A (en) * | 2008-04-02 | 2009-10-29 | Panasonic Corp | Method for synthesizing tin phosphate |
| CN102024948A (en) * | 2009-09-10 | 2011-04-20 | 比亚迪股份有限公司 | Tin-based composite oxide material as well as preparation method and application thereof |
| CN103367741B (en) * | 2012-03-26 | 2016-04-27 | 比亚迪股份有限公司 | A kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery |
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2017
- 2017-12-01 CN CN201711248795.8A patent/CN109873125B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101483234A (en) * | 2008-01-08 | 2009-07-15 | 三星Sdi株式会社 | Electrode assembly and lithium secondary battery having the same |
| JP2009249194A (en) * | 2008-04-02 | 2009-10-29 | Panasonic Corp | Method for synthesizing tin phosphate |
| CN102024948A (en) * | 2009-09-10 | 2011-04-20 | 比亚迪股份有限公司 | Tin-based composite oxide material as well as preparation method and application thereof |
| CN103367741B (en) * | 2012-03-26 | 2016-04-27 | 比亚迪股份有限公司 | A kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| "Elimination of Extraneous Irreversible Capacity in Mesoporous Tin Phosphate Anode by Amorphous Carbon Coating ";Eunjin Kim et al.;《Electrochemical and Solid-State Letters》;20060118;摘要，第156页第2栏 * |
| "Synthesis of a novel mesoporous tin phosphate, SnPO4";Nawal Kishor Mal et al.;《ChemComm》;20020107;第112-113页 * |
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