CN114420936B - Nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material and preparation method thereof - Google Patents

Nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material and preparation method thereof Download PDF

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CN114420936B
CN114420936B CN202210318548.5A CN202210318548A CN114420936B CN 114420936 B CN114420936 B CN 114420936B CN 202210318548 A CN202210318548 A CN 202210318548A CN 114420936 B CN114420936 B CN 114420936B
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刘翠荣
赵为刚
阴旭
徐大伟
杨兰栋
孟员员
孟庆森
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Shanxi Polyene Technology Co ltd
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Abstract

The invention discloses a nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material and a preparation method thereof2/EG) composite material. The obtained SnO2Mixing EG powder and sodium hypophosphite uniformly, heating in inert atmosphere, and building sandwich type Sn in situ by one-step phosphating method4P3an/EG composite material. The mass ratio of the tin tetrachloride pentahydrate to the nitrogen-doped expanded graphite is 3.5: (0.355-1); the mass ratio of the tin oxide/nitrogen-doped expanded graphite composite material to the sodium hypophosphite is 1: 5. The electrode material has high cyclic specific capacity and excellent cyclic stability, and has good application prospect. The preparation process of the composite cathode material is simple and controllable, is convenient to operate, and is suitable for industrial production.

Description

Nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of lithium ion battery electrode materials, and particularly relates to a nitrogen-doped expanded graphite/tin phosphide multilayer composite material and a preparation method thereof.
Background
With the rapid development of portable electronic equipment and power automobile industries, the market demand for energy carriers with high energy density, long cycle life, low cost and good safety performance is increasing day by day, and the graphite widely used at present cannot meet the market demand of rapid development at present due to lower theoretical capacity and energy density. The search for materials with higher energy density, high power density and low price becomes the key point of the research of the current cathode materials.
The phosphorus-based material has very obvious competitive advantage due to high energy density, and as an alloy type cathode material, the rate capability of the phosphorus-based material is greatly improved by an alloying energy storage mechanism, so that the phosphorus-based material has very wide application prospect. However, the phosphorus-based material has a large volume expansion rate in the charging and discharging processes, which leads to a significant reduction in capacity, and the conductivity of the phosphorus-based material also needs to be further improved. Research shows that the metal phosphide formed by combining the phosphorus element and the conductive metal element can effectively improve the electrochemical performance and stability of the phosphorus-based material.
Tin phosphide (Sn)4P3) The layered semiconductor material is formed by alternately stacking tin atoms and phosphorus atoms, has good electrochemical activity, higher theoretical specific capacity and good cycling stability. Sn (tin)4P3Sn is combined with P, so that a synergistic lithium storage mechanism of Sn and P is realized, the high conductivity of Sn makes up the weak point of poor conductivity of P, and Li generated by charge-discharge reaction3The P phase can also serve as a protective matrix to prevent aggregation of Sn, and the synergistic effect of Sn and P can relieve volume expansion and prevent electrochemical aggregation, so that the chemical stability in the material is ensured, and the advantages determine that the tin phosphide is a cathode material with a great development prospect. The tin phosphide is subjected to nanocrystallization design, so that the specific surface area can be increased while the advantages of the tin phosphide structure and chemical properties are exerted, the stress generated by ion deintercalation is coordinated, and the electrochemical properties of the material are further improved by shortening an ion transmission path and the like. However, the material still has the problems of volume expansion, poor intrinsic electronic conductivity, low utilization rate of active substances and the like in the circulating process.
In the prior art, for example, a Chinese patent with an application authorization number of CN110993913A discloses a preparation method of a tin phosphide/expanded graphite cathode composite material of a sodium ion battery, the tin phosphide is prepared by phosphorizing a tin hydroxide precursor through a hydrogen phosphide phase, then a graphite flake stripped from expanded graphite is wrapped on the surface of the tin phosphide through ball milling, and the tin hydroxide precursor is prepared through a sol-gel method. The mass percentage content of the expanded graphite is 10-30%. The preparation method has complex process, higher energy consumption and higher time and economic cost, thereby being not beneficial to marketization application.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a nitrogen-doped layer-extended graphite/tin phosphide multilayer composite electrode material with excellent electrochemistry and good stability and a preparation method thereof, aiming at the problems that tin phosphide in the prior art has low capacity retention rate in the charging and discharging processes and electrode pulverization is caused by volume expansion.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material is prepared by oxidizing nitrogen-doped expanded-layer graphite by a graphite Hummer method and then reducing the oxidized nitrogen-doped expanded-layer graphite by annealing, wherein the interlayer spacing is 3.7-4.3A; the raw material for synthesizing the tin phosphide is SnCl4·5H2O、NaH2PO2The composite electrode material is filled in an interlayer of nitrogen-doped expanded graphite through in-situ growth and attached to the nitrogen-doped expanded graphite layer in a coating state, the structure of the nitrogen-doped expanded graphite/tin phosphide multilayer composite electrode material is a multilayer structure of a graphite layer-tin phosphide-graphite layer, the conductivity of the material is improved by the expanded graphite layer of the interlayer structure, and the tin phosphide is attached to the interlayer, so that lithium ion de-intercalation sites are provided by graphite, and lithium storage sites can also be provided by the tin phosphide at the same time, and a good synergistic effect is achieved. Under the protection of the graphite layer, volume expansion of tin phosphide in the charging and discharging process is effectively prevented. The size of the tin phosphide is in the nanometer level, and the tin phosphide is uniformly dispersed in the interlayer of the nitrogen-doped expanded graphite to finally obtain the nitrogen-doped expanded graphite/tin phosphide multilayer composite electrode material.
The invention relates to a nitrogen-doped expanded graphite/tin phosphide multilayer composite electrode material, which is a two-step lithium storage mechanism:
and (3) discharging: sn (tin)4P3 + 9Li+ + 9e-↔ 4Sn + 3Li3P (1)
2Sn + 5Li+ + 5e- ↔ Li5Sn2 (2)
6C+xLi++xe-↔LiXC6 (3)
And (3) charging process: li5Sn2 ↔ 2Sn + 5Li+ + 5e– (1)
4Sn + 3Li3P ↔ Sn4P3+ 9Li+ + 9e– (2)
LiXC6↔6C+xLi++xe- (3)
The invention also relates to a preparation method of the nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material, which comprises the following steps:
1) weighing graphite powder with a certain mass, adding concentrated sulfuric acid, stirring in an ice bath, slowly adding potassium permanganate, stirring after adding, and transferring to a water bath kettle to continue stirring; transferring to an ice bath, continuously stirring, slowly adding water, dropwise adding hydrogen peroxide (30%) after the water is added, performing suction filtration after stirring for three hours to obtain a khaki precipitate, washing to be neutral, and drying for later use;
2) keeping the product obtained in the step 1) in a tubular furnace at 600 ℃ for 1h, and heating at the speed of 5 ℃ for min-1Cooling to room temperature
Grinding to obtain nitrogen-doped expanded graphite;
3) weighing a certain mass of tin tetrachloride pentahydrate and nitrogen-doped expanded graphite, putting the tin tetrachloride pentahydrate and the nitrogen-doped expanded graphite into a hydrosolvent, carrying out constant-temperature ultrasonic treatment at the temperature of 20-40 ℃, and then carrying out hydrothermal reaction to obtain a tin oxide/nitrogen-doped expanded graphite composite material;
4) mixing the product obtained in the step 3) with sodium hypophosphite, grinding and sintering for phosphorization; washing the product with hydrochloric acid, then washing the product with deionized water to neutrality, washing the product with alcohol, and drying the product to obtain the nitrogen-doped layer-expanding graphite/tin phosphide multilayer composite material.
Preferably, the mass ratio of the tin tetrachloride pentahydrate to the nitrogen-doped exfoliated graphite in the step 3) is 3.5 (1-0.355).
Preferably, the mass ratio of the tin oxide/nitrogen-doped layer-expanding graphite composite material to the sodium hypophosphite in the step 4) is 1: 5.
Preferably, the mass percent of the tin phosphide is 58.67-80%.
Preferably, the hydrothermal reaction temperature is 80-120 ℃ and the reaction time is 10-12 h.
Preferably, the phosphating temperature in the step 3) is 280 ℃, and N is introduced2Protecting, and keeping the temperature for 15-30 min.
Compared with the prior art, the invention provides a nitrogen-doped expanded graphite/tin phosphide multilayer composite material and a preparation method thereof, and the composite material has the following advantages:
1) the nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material prepared by the invention has simple preparation process, controllable working procedure and industrialized production,
2) the nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material prepared by the invention has higher cycling stability and high specific capacity.
3) The nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material prepared by the invention uses the nitrogen-doped expanded-layer graphite as a matrix, and the tin phosphide/expanded-layer multilayer composite structure is constructed by an in-situ growth method, so that the conductivity of the material is effectively improved.
4) The nitrogen-doped expanded graphite/tin phosphide multilayer composite material prepared by the invention is prepared by mixing nano Sn4P3The carbon nano-particles are uniformly dispersed in a nitrogen-doped expanded graphite matrix, so that the problem of electrode material pulverization caused by large volume expansion in the charge-discharge cycle process is effectively prevented, and the cycle stability of the carbon nano-particles is enhanced.
Drawings
FIG. 1 is a SEM image of a nitrogen-doped exfoliated graphite/tin phosphide multilayer composite material;
FIG. 2 is a charge-discharge cycle chart of the electrode materials of example 1, example 2 and comparative example 1;
FIG. 3 is a graph showing the charge-discharge rate of a nitrogen-doped exfoliated graphite/tin phosphide multilayer composite material;
FIG. 4 is a cyclic voltammogram of a nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material;
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that, without departing from the concept of the present invention, several improvements and extensions can be made, all of which shall fall within the protection scope of the present invention:
example 1
Preparation of nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material
1) Weighing 5g of graphite powder, adding 50ml of concentrated sulfuric acid, stirring in an ice bath, slowly adding 7g of potassium permanganate, stirring for 15min after the addition is finished, transferring to a water bath kettle, stirring for 5h at 36 ℃. And then transferring to an ice bath, stirring, slowly adding 200ml of water, dropwise adding about 3ml of hydrogen peroxide (30%) after the water is added, performing suction filtration after stirring for three hours to obtain a khaki precipitate, washing to be neutral, and drying for later use.
2) Keeping the product obtained in the step 1) in a tubular furnace at 600 ℃ for 1h, and heating at the speed of 5 ℃ for min-1And cooling to room temperature and grinding to obtain the nitrogen-doped expanded graphite.
3) Weighing 3g of ethylenediamine and 3g of nitrogen-doped expanded graphite, putting the materials into a hydrosolvent, carrying out constant temperature ultrasonic treatment at 20-40 ℃, carrying out hydrothermal reaction for 3h at 80 ℃, adding 6g of stannic chloride pentahydrate, continuing the hydrothermal reaction for 6h at 130 ℃, and drying to obtain a tin oxide/nitrogen-doped expanded graphite composite material;
4) mixing the product obtained in the step 3) with sodium hypophosphite, grinding, and sintering at 280 ℃ for 5 min; the product is mixed with 0.1 mol.L-1And (3) washing with hydrochloric acid, then washing with deionized water to neutrality, washing with alcohol, and drying to obtain the nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material.
The nitrogen-doped expanded graphite/tin phosphide multilayer composite material is used as an active material, NMP and DMF are used as diluents, PVDF is used as a binder, and the weight percentages of the active material: conductive agent: PVDF (polyvinylidene fluoride) mass ratio of 8: 1: 1, preparing the button cell to test the circulating specific capacity and the rate capability of the button cell. The results showed that the current density was 0.5 A.g-1It has 526mAh ∙ g-1The specific capacity of (A). The capacity retention rate is close to 100 percent when the resin is cycled for 200 times. As shown in SEM of FIG. 1Nanometer flower-shaped tin phosphide grows in the nitrogen-doped expanded-layer graphite interlayer, and the element content of the nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material is shown in table 1, wherein the element content of the carbon element is 70%, the element content of the P element is 10.4%, the element content of the N element is 5.5%, and the element content of the S element is 14.1%, so that the process can be used for preparing a more stable nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite electrode material. Fig. 4 is a cyclic voltammogram of nitrogen-doped exfoliated graphite/tin phosphide, the electrochemical performance of the composite material is also taken as a half-cell structure, and in the first cathodic scan, the peak at 0.82V can be attributed to the initial reaction of lithium and phosphorus, exfoliated graphite: sn (tin)4P3 + 9Li+ + 9e-↔ 4Sn + 3Li3P，6C+xLi++xe-↔LiXC6. Another reduction peak of 0.52V indicates the formation of an SEI film. A very small reduction peak around 0.25V can be attributed to the alloying reaction between Li and Sn: 2Sn + 5Li++ 5e- → Li5Sn2. As for the charging process, three broad anodic peaks with Li observed at 0.6 and 1.18VxSn、LiXC6And Li3The decomposition of P is related to: are each Li5Sn2→2Sn + 5Li+ + 5e-、4Sn + 3Li3P →Sn4P3 + 9Li+ + 9e-、LiXC6↔6C+xLi++ xe-。
TABLE 1
Figure 195333DEST_PATH_IMAGE001
Example 2
Preparation of nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material
1) Weighing 6g of stannic chloride pentahydrate and 3g of graphite, putting into a hydrosolvent, carrying out constant-temperature ultrasonic treatment at 20-40 ℃, and carrying out hydrothermal reaction at 80 ℃ for 12h to obtain a stannic oxide/nitrogen-doped expanded graphite composite material;
2) mixing the product of step 1) with sodium hypophosphite, grinding, and thenThen sintering at 280 ℃ for 5 min; the product is mixed with 0.1 mol.L-1And (3) washing with hydrochloric acid, then washing with deionized water to neutrality, washing with alcohol, and drying to obtain the graphite/tin phosphide composite electrode material. The graphite layers have low spacing, and the tin phosphide can only be simply coated and cannot form a stable multilayer structure on the surface layer.
The graphite/tin phosphide composite electrode material is used as an active material, NMP is used as a diluent, PVDF is used as a binder, and the weight ratio of the active material: conductive agent: PVDF (polyvinylidene fluoride) mass ratio of 8: 1: 1, preparing the button cell to test the circulating specific capacity and the rate capability of the button cell. The results showed that the current density was 0.5 A.g-1When it is used, it has 345mAh ∙ g-1The specific capacity of (A). But the specific capacity is seriously reduced when the material is circulated to 150 circles, which indicates that the graphite/tin phosphide composite material fails in the circulation process and cannot form a good synergistic effect with graphite, and the capacity retention rate of the material is close to 35% when the material is circulated for 200 times. After the micro-layer-expanding treatment, the first coulombic efficiency of the graphite/tin phosphide composite material is increased to 92.7% from 91.6%, the reversible capacity is increased to 379.8 mA/g from 345.5 mAh/g, the cycle life and the rate discharge performance are effectively improved, the lithium intercalation potential of the nitrogen-doped layer-expanded graphite is slightly increased, lithium ions are easy to be separated from graphite layers, and the average interlayer spacing of the graphite is coated by tin phosphide, the interlayer spacing is moderate, and the activation energy of the graphite lithium-removing reaction is obviously improved.
Comparative example 1:
and (3) taking the no-load graphite as a comparison material, preparing the button cell according to the same proportion under the same condition, and testing the cyclic specific capacity and the rate capability of the button cell. The graphite material of comparative example 1 was prepared into a lithium ion battery, and a charge-discharge test was performed using a blue system at 0.5A · g-1The specific capacity under the current density is 252mAhg-1The capacity retention rate was 93%.
Comparative example 2:
and (3) taking nitrogen-doped expanded graphite as a comparison material, preparing the button cell according to the same proportion under the same condition, and testing the cyclic specific capacity and the rate capability of the button cell. The charge and discharge test is carried out by adopting a blue electric system, and the charging and discharging time is 0.5 A.g-1The specific capacity under the current density is 278mAhg-1The capacity retention rate was 95%. Description of the graphite MaterialAfter the micro-layer expansion treatment, the rate capability is effectively improved. This is presumably because, after the interlayer spacing of graphite is slightly increased, the force field formed by carbon atoms therein is changed, and this change may cause the activation energy (potential barrier) of the intercalation and deintercalation reaction of graphite to be reduced, so that the resistance of the deintercalation process of lithium ions from the graphite layers is reduced, and therefore, the deintercalation rate of lithium ions from the graphite layers is higher, the lithium ions are more easily deintercalated from the graphite layers, and macroscopically, the large-current charge and discharge performance of the battery is significantly improved.
The nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite electrode material has good synergistic effect and cycling stability. The electrode material has high cyclic specific capacity and excellent cyclic stability, and has good application prospect. The preparation process of the composite cathode material is simple and controllable, is convenient to operate, and is suitable for industrial production.
The foregoing is illustrative of the present patent, and is not intended to limit the scope of the patent, which is defined by the claims appended hereto, as they are regarded as illustrative of the present patent.

Claims (8)

1. The nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material is characterized in that the nitrogen-doped expanded layer is
The method comprises the steps of oxidizing graphite by a graphite Hummer method, annealing and reducing to obtain nitrogen-doped expanded graphite, introducing a nitrogen source for doping in the in-situ growth process of tin phosphide, filling the tin phosphide in an interlayer of the nitrogen-doped expanded graphite through in-situ growth, attaching the tin phosphide to a graphite layer in a coating state, and constructing the tin phosphide/nitrogen-doped expanded graphite electrode material by uniformly dispersing the tin phosphide/nitrogen-doped expanded graphite electrode material in a nitrogen-doped graphite interlayer with the average interlayer spacing d002 value of 0.3366 nm, wherein the structure of the nitrogen-doped expanded graphite/tin phosphide multilayer composite electrode material is a multilayer structure of a nitrogen-doped graphite layer-tin phosphide-nitrogen-doped graphite layer, and the tin phosphide/nitrogen-doped expanded graphite electrode material is constructed.
2. A preparation method of a nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material comprises the following steps:
1) weighing graphite powder with a certain mass, adding concentrated sulfuric acid, stirring in an ice bath, slowly adding potassium permanganate, stirring after adding, and transferring to a water bath kettle to continue stirring; transferring to an ice bath, continuously stirring, slowly adding water, dropwise adding hydrogen peroxide (30%) after the water is added, performing suction filtration after stirring for three hours to obtain a khaki precipitate, washing to be neutral, and drying for later use;
2) keeping the product obtained in the step 1) in a tubular furnace at 600 ℃ for 1h, and heating at the speed of 5 ℃ for min-1Introducing nitrogen gas from two ends, performing bidirectional opposite blowing at the speed of 0.05 m/h, cooling to room temperature, and grinding to obtain nitrogen-doped expanded graphite;
3) weighing a certain mass of tin tetrachloride pentahydrate, nitrogen-doped expanded graphite and ethylenediamine, putting into a water solvent, carrying out constant-temperature ultrasonic treatment at 20-40 ℃, and then carrying out hydrothermal reaction to obtain a tin oxide/nitrogen-doped expanded graphite composite material;
4) and (3) mixing and grinding the product obtained in the step 3) with sodium hypophosphite, sintering and phosphorizing, washing with hydrochloric acid after phosphorization, washing with deionized water to be neutral, washing with alcohol, and drying to finally obtain the nitrogen-doped layer-expanding graphite/tin phosphide multilayer composite electrode material.
3. The method for preparing the nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material as claimed in claim 2, wherein the mass ratio of the tin tetrachloride pentahydrate to the nitrogen-doped expanded-layer graphite in the step 3) is 3.5 (1-0.355).
4. The method for preparing the nitrogen-doped layer-expanding graphite/tin phosphide multilayer composite material as claimed in claim 2, wherein in the step 3), the ethylenediamine and the layer-expanding graphite are preferentially added into the aqueous solvent, and are placed in the polytetrafluoroethylene liner for hydrothermal reaction at 120 ℃ for 2 hours, and then the tin tetrachloride pentahydrate is added for hydrothermal reaction at 135.5-160 ℃ for continuous reaction for 3 hours.
5. The method for preparing the nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material according to claim 2, wherein the mass ratio of the tin oxide/nitrogen-doped expanded-layer graphite composite material to the sodium hypophosphite in the step 4) is 1: 5.
6. The preparation method of the nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material as claimed in claim 2, wherein the mass percent of the tin phosphide is 58.67% -80%.
7. The preparation method of the nitrogen-doped layer-expanded graphite/tin phosphide multilayer composite material as claimed in claim 2, wherein the hydrothermal reaction temperature is 80-120 ℃ and the reaction time is 10-12 h.
8. The method for preparing the nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material as claimed in claim 2, wherein the phosphating temperature in the step 3) is 280 ℃, and N is introduced2Protecting, and keeping the temperature for 15-30 min.
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