CN107834044B - Graphene-based lithium iron phosphate composite material and application thereof - Google Patents
Graphene-based lithium iron phosphate composite material and application thereof Download PDFInfo
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Abstract
The invention relates to a graphene-based lithium iron phosphate composite material and application thereof. The preparation method of the composite material comprises the following steps: mixing a lithium compound, phosphate, ferric salt, graphite and an intercalation agent with water to prepare graphene slurry; adding hydrogen peroxide and a nitrogen source into the graphene slurry, and mixing to prepare precursor slurry; carrying out hydrothermal reaction on the precursor slurry to obtain hydrogel; and soaking the hydrogel in an organic carbon source solution, separating, and sintering in a reducing atmosphere to obtain the hydrogel. In the composite material, the nitrogen source plays a role in doping modification and can form a C-N bond with graphene to improve the conductivity of the composite material; through the water absorption effect of the hydrogel, organic carbon sources can be adsorbed in and on the surface of the composite material, porous carbon is formed after sintering, the porous carbon has the effects of improving the electric conductivity and the liquid absorption and retention capacity, the composite material has the characteristics of good electric conductivity and high tap density due to the comprehensive effect of the substances, and the rate capability and gram volume exertion of the lithium iron phosphate composite material are obviously improved.
Description
Technical Field
The invention belongs to the field of lithium ion battery electrode materials, and particularly relates to a graphene-based lithium iron phosphate composite material and application thereof.
Background
The lithium iron phosphate material is a main commercialized material of the lithium ion battery by virtue of the advantages of high safety performance, environmental friendliness, long cycle life and the like, but the material has the defects of low gram capacity, poor rate capability, poor conductivity and the like, and the application of the material in the field of high-specific energy density and fast-charging lithium ion batteries is limited. The lithium iron phosphate material is coated and modified so as to improve gram capacity exertion and electron conduction rate of the material, and the method becomes one of the directions for improving the lithium iron phosphate material.
The application publication number of CN106602006A discloses a graphene lithium iron phosphate composite material, which uses a lithium iron phosphate precursor and graphene as raw materials, and prepares lithium iron phosphate and the graphene coated on the surface of the lithium iron phosphate through ultrasonic dispersion, drying and reduction sintering. The graphene layer and the lithium iron phosphate of the graphene lithium iron phosphate composite material are combined together through an adsorption effect, and the defects of poor conductivity, low tap density and the like still exist, so that the rate capability and gram volume performance of the material are required to be further improved.
Disclosure of Invention
The invention aims to provide a graphene-based lithium iron phosphate composite material, and solves the problems of poor rate capability and low gram volume of the existing lithium iron phosphate composite material.
The second purpose of the present invention is to provide an application of the graphene-based lithium iron phosphate composite material as a positive electrode material of a lithium ion battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the graphene-based lithium iron phosphate composite material is prepared by the following steps:
1) mixing a lithium compound, phosphate, ferric salt, graphite and an intercalation agent with water to prepare graphene slurry;
2) adding hydrogen peroxide and a nitrogen source into the graphene slurry, and mixing to prepare precursor slurry;
3) carrying out hydrothermal reaction on the precursor slurry to obtain hydrogel;
4) soaking the hydrogel in an organic carbon source solution, carrying out solid-liquid separation, and sintering the solid phase in a reducing atmosphere to obtain the hydrogel.
According to the graphene-based lithium iron phosphate composite material provided by the invention, hydrogen peroxide and a nitrogen source are added into graphene slurry for hydrothermal reaction, the hydrogen peroxide has a weak oxidation effect and can introduce reactive groups such as hydroxyl, carboxyl and the like into the surface of the graphene material, after the hydrothermal reaction, the reactive groups of the graphene material and cations in phosphate form a composite hydrogel with chemical bonds, a high-density graphene lithium iron phosphate precursor with nano holes is formed after drying, and then the graphene-based lithium iron phosphate composite material is prepared by sintering in a reducing atmosphere.
In the composite material, the nitrogen source plays a role in doping modification and can form a C-N bond with graphene to improve the conductivity of the composite material; the composite material has the characteristics of good conductivity and high tap density due to the comprehensive action of the substances, and the rate capability and gram volume exertion of the lithium iron phosphate composite material are obviously improved.
In the step 1), the molar ratio of the lithium compound, the phosphate, the ferric salt, the intercalation agent and the graphite is (1-1.5): 1: 1: (0.1-3): (1-10). In the step, in order to be convenient for uniform mixing, a lithium compound, an iron salt and a phosphate can be dissolved in water to prepare a mixed solution A; mixing graphite, an intercalation agent and water to prepare a mixed solution B, mixing the mixed solution A and the mixed solution B, and performing ultrasonic dispersion to prepare the graphene slurry.
The lithium compound is lithium carbonate and/or lithium hydroxide. The phosphate is M
3PO
4、M
2HPO
4、MH
2PO
4M is sodium, potassium or ammonium. The graphite is preferably flake graphite. The intercalation agent is sodium hypochlorite.
In the step 2), the mass ratio of the graphite raw material to the hydrogen peroxide and the nitrogen source in the graphene slurry is (4-12): (0.01-0.3): (0.08-0.6) and the mass concentration of the hydrogen peroxide is 1-30%.
In the step 2), the nitrogen source is at least one of pyrrole, ammonia water, aniline, urea and melamine, and the mass concentration of the ammonia water is 1-30%.
In the step 3), the hydrothermal reaction is carried out for 2-6 h at 150-200 ℃.
In the step 4), the organic carbon source is at least one of phenolic resin, glucose, sucrose, starch and citric acid. The mass concentration of the organic carbon source solution is 1-5%. The soaking time is 6-24 h. And separating out hydrogel after soaking, drying for 24-72 h at 40-60 ℃ to obtain dry gel, and sintering the dry gel in a reducing atmosphere.
In the step 4), the reducing atmosphere is a hydrogen atmosphere. And the sintering is carried out for 6-12 h at the temperature of 600-900 ℃.
The graphene-based lithium iron phosphate composite material is used as a lithium ion battery positive electrode material, has the characteristics of high conductivity and high tap density, and can remarkably improve the rate capability and gram volume exertion of a lithium iron phosphate material.
Drawings
Fig. 1 is an SEM image of the lithium iron phosphate graphene composite prepared in example 1.
Detailed Description
The following examples are provided to further illustrate the practice of the invention.
Example 1
The graphene-based lithium iron phosphate composite material of the embodiment is prepared by the following steps:
1) 8.88g (0.12mol) of lithium carbonate and 27.8g (0.1mol) of FeSO were mixed together
4·7H
2Dissolving O and 11.5g (0.1mol) of ammonium dihydrogen phosphate in 500ml of water to prepare a mixed solution A;
mixing 4.8g of crystalline flake graphite, 14.8g (0.2mol) of sodium hypochlorite intercalation agent and 500ml of water to prepare a mixed solution B;
mixing the mixed solution A and the mixed solution B, performing ultrasonic dispersion for 12 hours, and centrifuging to remove floating impurities to obtain lower graphene slurry;
2) adding 0.11ml of hydrogen peroxide (with the mass concentration of 10%) and 0.22g of pyrrole into the graphene slurry, stirring and mixing, then transferring to a high-pressure reaction kettle, carrying out hydrothermal reaction for 4 hours at 180 ℃, and separating to obtain hydrogel;
3) soaking the hydrogel in 176ml of 1% glucose solution for 12h, separating, and drying at 50 ℃ for 48h to obtain xerogel;
4) and transferring the dried gel into a tubular furnace, sintering for 8h at 800 ℃ in a hydrogen atmosphere, cooling to room temperature, crushing and grinding to obtain the graphene-based lithium iron phosphate anode material.
Example 2
The graphene-based lithium iron phosphate composite material of the embodiment is prepared by the following steps:
1) dissolving 2.4g (0.1mol) of lithium hydroxide, 14.3g (0.1mol) of ferrous oxalate and 13.2g (0.1mol) of diammonium phosphate in 500ml of water to prepare a mixed solution A;
mixing 12g of crystalline flake graphite, 0.74g (0.01mol) of sodium hypochlorite intercalation agent and 500ml of water to prepare a mixed solution B;
mixing the mixed solution A and the mixed solution B, performing ultrasonic dispersion for 24 hours, and centrifuging to remove floating impurities to obtain lower graphene slurry;
2) adding 0.016g of hydrogen peroxide (with the mass concentration of 1%) and 0.08g of urea into the graphene slurry, stirring and mixing, then transferring to a high-pressure reaction kettle, carrying out hydrothermal reaction for 6 hours at 150 ℃, and separating to obtain hydrogel;
3) soaking the hydrogel in 80ml of 1% starch solution for 24h, separating, and drying at 40 ℃ for 72h to obtain xerogel;
4) and transferring the dried gel into a tubular furnace, sintering for 12h at 600 ℃ in a hydrogen atmosphere, cooling to room temperature, crushing and grinding to obtain the graphene-based lithium iron phosphate anode material.
Example 3
The graphene-based lithium iron phosphate composite material of the embodiment is prepared by the following steps:
1) 11.1g (0.15mol) of lithium carbonate and 27.8g (0.1mol) of FeSO were mixed together
4·7H
2Dissolving O and 20.3g (0.1mol) of ammonium phosphate in 500ml of water to prepare a mixed solution A;
mixing 6g of crystalline flake graphite, 22.2g (0.3mol) of sodium hypochlorite intercalation agent and 500ml of water to prepare a mixed solution B;
mixing the mixed solution A and the mixed solution B, performing ultrasonic dispersion for 48 hours, and centrifuging to remove floating impurities to obtain lower graphene slurry;
2) adding 0.31g of hydrogen peroxide (with the mass concentration of 30%) and 0.62g of ammonia water (with the mass concentration of 10%) into the graphene slurry, stirring and mixing, then transferring into a high-pressure reaction kettle, carrying out hydrothermal reaction for 2 hours at 200 ℃, and separating to obtain hydrogel;
3) soaking the hydrogel in 31ml of 1% phenolic resin solution for 24h, separating, and drying at 60 ℃ for 24h to obtain xerogel;
4) and transferring the dried gel into a tubular furnace, sintering for 6h at 900 ℃ in a hydrogen atmosphere, cooling to room temperature, crushing and grinding to obtain the graphene-based lithium iron phosphate anode material.
In other embodiments of the graphene-based lithium iron phosphate cathode material of the present invention, the nitrogen source may be replaced with aniline and melamine in equal amounts, and the organic carbon source may be replaced with sucrose and citric acid in the same amounts according to the process steps and the addition of embodiment 1, so as to obtain a product with performance equivalent to that of embodiment 1.
Comparative example
The graphene-based lithium iron phosphate positive electrode material of the comparative example is prepared by the following method: 11.1g of lithium carbonate and 27.8g of FeSO
4·7H
2Adding O, 20.3g of ammonium phosphate and 0.31g of graphene into 500ml of secondary distilled water, performing ultrasonic dispersion uniformly, filtering, drying, transferring to a tubular furnace, calcining at 750 ℃ for 8h in a hydrogen atmosphere, naturally cooling to room temperature, crushing and grading to obtain the catalyst.
Test example 1
The experimental example observes the surface morphology of the graphene-based lithium iron phosphate positive electrode material of example 1, and an SEM image of the material is shown in fig. 1, which shows that the graphene-based lithium iron phosphate positive electrode material has uneven surface, rich pore structure, and high liquid absorption capacity.
Test example 2
In the test example, electrochemical performance tests were performed on the graphene-based lithium iron phosphate positive electrode materials of the examples and the comparative examples.
2.1 button cell test
Respectively weighing 2.0g of the lithium iron phosphate positive electrode materials of examples 1-3 and the comparative example, 0.1g of conductive carbon black and 0.1g of PVDF, mixing, adding 2.5g N-methyl pyrrolidone, and uniformly mixing to obtain positive electrode material slurry. Coating the anode material slurry on an aluminum foil (the coating thickness is 140 mu m), drying for 2h at 120 ℃ in vacuum, beating into 5mm round pieces by using a puncher, tabletting by using a tabletting machine under 10Mpa, keeping the temperature at 120 ℃ in vacuum for 12h, and weighing the weight of the anode pieces. The button cell is assembled in an argon-protected glove box, wherein the negative electrode is a metal lithium sheet, and the electrolyte is LiPF with the concentration of 1mol/L
6The solution (solvent mixed by EC and DEC in a volume ratio of 1: 1) has a diaphragm of Celgard2400 microporous polyethylene film.
The assembled button cell was tested for electrical performance on a blue tester, and charged/discharged at a constant current of 0.2C over a voltage range of 2.75V to 4.25V, and the discharge capacity and first efficiency were tested, with the results shown in table 1.
TABLE 1 results of the test for the electrification of each of the examples and comparative examples
| Item | Example 1 | Example 2 | Example 3 | Comparative example |
| First discharge capacity (mAh/g) | 162.2 | 161.3 | 160.3 | 153.5 |
| First efficiency (%) | 97.9 | 96.9 | 95.3 | 93.4 |
As can be seen from the results in table 1, the discharge capacity and the first efficiency of the lithium iron phosphate composite material prepared in the example are significantly higher than those of the comparative example, because the conductivity of the material can be effectively improved by the presence of nitrogen doping, a graphene network and a carbon source, thereby facilitating the improvement of gram capacity exertion and first efficiency improvement of the cathode material.
2.2 liquid absorption and retention test
The liquid absorbing and retaining ability of each of the examples and comparative examples was examined, and the results are shown in Table 2.
TABLE 2 comparison of liquid-absorbing and liquid-retaining capacities of examples and comparative examples
As can be seen from the results in table 2, the liquid absorbing and retaining capabilities of the examples are significantly higher than those of the comparative examples, which is because the lithium iron phosphate positive electrode material of the examples has a higher specific surface area, and abundant nano-pores can be formed during the soaking and drying processes of the hydrogel, which is helpful for further improving the liquid absorbing and retaining capabilities of the material.
2.3 pouch cell testing
Respectively taking the lithium iron phosphate composite materials prepared in the examples 1-3 and the comparative example as positive electrode materials, graphite as negative electrode materials and LiPF with the concentration of 1mol/L
6A5 Ah soft package battery is prepared by taking a solution (formed by mixing EC and DEC in a volume ratio of 1: 1) as an electrolyte and a Celgard2400 membrane as a diaphragm, and the rate performance and the cycle performance are detected, wherein the results are shown in Table 3.
TABLE 3 comparison of electrochemical Properties of examples and comparative examples
As can be seen from the results in table 3, the rate capability and cycle performance of the lithium ion battery of the embodiment are far better than those of the comparative example, because the conductivity of electrons in the charging and discharging process is effectively improved by the graphene-based lithium iron phosphate positive electrode material, and the hydrogel can form rich holes through soaking and drying processes, has a stable structure and a strong liquid absorption capability, thereby effectively improving the cycle performance and high rate charging and discharging performance of the prepared lithium ion battery.
Claims (10)
1. The graphene-based lithium iron phosphate composite material is characterized by being prepared by the following steps:
1) mixing a lithium compound, phosphate, ferric salt, graphite and an intercalation agent with water to prepare graphene slurry;
2) adding hydrogen peroxide and a nitrogen source into the graphene slurry, and mixing to prepare precursor slurry;
3) carrying out hydrothermal reaction on the precursor slurry to obtain hydrogel;
4) soaking the hydrogel in an organic carbon source solution, carrying out solid-liquid separation, and sintering a solid phase in a reducing atmosphere to obtain the hydrogel;
wherein the ferric salt in the step 1) is ferrous sulfate or ferrous oxalate;
in the step 4), the organic carbon source is at least one of phenolic resin, glucose, sucrose, starch and citric acid; the reducing atmosphere is a hydrogen atmosphere.
2. The lithium iron phosphate graphene-based composite material according to claim 1, wherein in the step 1), the molar ratio of the lithium compound, the phosphate, the iron salt, the intercalation agent and the graphite is (1-1.5): 1: 1: (0.1-3): (1-10).
3. The lithium iron phosphate graphene-based composite material according to claim 1 or 2, wherein the lithium compound is lithium carbonate and/or lithium hydroxide.
4. The lithium iron phosphate graphene-based composite material according to claim 1 or 2, wherein the phosphate is M
3PO
4、M
2HPO
4、MH
2PO
4M is ammonium.
5. The lithium iron phosphate graphene-based composite material according to claim 1 or 2, wherein the intercalating agent is sodium hypochlorite.
6. The graphene-based lithium iron phosphate composite material according to claim 1, wherein in the step 2), the mass ratio of the graphite raw material to the hydrogen peroxide and nitrogen source in the graphene slurry is (4-12): (0.01-0.3): (0.08-0.6) and the mass concentration of the hydrogen peroxide is 1-30%.
7. The lithium iron phosphate graphene composite material according to claim 1 or 6, wherein in the step 2), the nitrogen source is at least one of pyrrole, ammonia water, aniline, urea and melamine, and the mass concentration of the ammonia water is 1-30%.
8. The lithium iron phosphate graphene composite material according to claim 1, wherein in the step 3), the hydrothermal reaction is performed at 150-200 ℃ for 2-6 h.
9. The lithium iron phosphate graphene composite material according to claim 1, wherein in the step 4), the sintering is performed at 600-900 ℃ for 6-12 h.
10. Use of the graphene-based lithium iron phosphate composite according to claim 1 as a positive electrode material for a lithium ion battery.
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| CN101800310A (en) * | 2010-04-02 | 2010-08-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing graphene-doped anode material for lithium-ion batteries |
| CN102169986A (en) * | 2011-04-02 | 2011-08-31 | 江苏乐能电池股份有限公司 | Preparation method of lithium ferric phosphate / grapheme composite positive electrode material |
| CN102447110A (en) * | 2011-12-14 | 2012-05-09 | 哈尔滨工业大学 | Preparation method of carbon nanomaterial-doped spherical iron phosphate and preparation method of carbon nanomaterial-doped lithium iron phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101800310A (en) * | 2010-04-02 | 2010-08-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing graphene-doped anode material for lithium-ion batteries |
| CN102169986A (en) * | 2011-04-02 | 2011-08-31 | 江苏乐能电池股份有限公司 | Preparation method of lithium ferric phosphate / grapheme composite positive electrode material |
| CN102447110A (en) * | 2011-12-14 | 2012-05-09 | 哈尔滨工业大学 | Preparation method of carbon nanomaterial-doped spherical iron phosphate and preparation method of carbon nanomaterial-doped lithium iron phosphate |
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