CN111211313B - Plant cellulose modified silicon/carbon composite negative electrode material and preparation method thereof - Google Patents

Plant cellulose modified silicon/carbon composite negative electrode material and preparation method thereof Download PDF

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CN111211313B
CN111211313B CN202010097626.4A CN202010097626A CN111211313B CN 111211313 B CN111211313 B CN 111211313B CN 202010097626 A CN202010097626 A CN 202010097626A CN 111211313 B CN111211313 B CN 111211313B
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马少宁
王兴蔚
侯佼
侯春平
贺超
杨丹
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Bolt New Materials Yinchuan Co ltd
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Abstract

The invention relates to a plant cellulose modified silicon/carbon composite negative electrode material and a preparation method thereof. The adsorption of silicon particles on the surface of a fiber extract is enhanced by utilizing the combined action of plant cellulose surface porosity and the compatibility of the plant cellulose and PEG, the agglomeration of nano silicon particles is inhibited, the plant cellulose is subjected to high-energy ball milling to form a fibrous lamellar structure, a lamellar and soft carbon structure after fiber carbonization is formed through high-temperature treatment, and the fibrous lamellar structure carbide is doped in a silicon-carbon composite material, so that the volume change of silicon in the lithium intercalation/deintercalation process is effectively reduced, the rapid capacity attenuation caused by the loss of electric contact between electrode materials due to structural collapse and pulverization in the repeated charge and discharge process of the silicon is inhibited, the electric conductivity of the composite material and the structural stability in the charge and discharge process of the silicon-carbon composite negative electrode material are enhanced, and the cycle performance of the silicon-carbon composite negative electrode material is improved.

Description

Plant cellulose modified silicon/carbon composite negative electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a plant cellulose modified silicon/carbon composite negative electrode material.
Background
The cathode material is used as an important component of the lithium ion battery, and has important significance on the performance and the cost of the battery. The current commercialized graphite-based and modified lithium ion battery cathode material thereof accounts for more than 97% of market share, but the application of the graphite-based and modified lithium ion battery cathode material in the fields of large-scale energy storage devices and power batteries is limited by the defects of low specific capacity, poor rate capability and the like.
The simple substance silicon is used as the lithium battery negative electrode material, the theoretical specific capacity is 4200mAh/g, the specific capacity of silicon oxide is 2400-2700mAh/g, the content of the silicon element in the earth crust accounts for 26.4 percent of the earth crust, the storage capacity is very rich, and the silicon material is safe and non-toxic, so that the silicon material has the advantages of low cost and environmental friendliness when being used as the lithium battery negative electrode material. However, as a negative electrode material, silicon undergoes a volume change of more than 300% during lithium intercalation/deintercalation, and the structure collapses and pulverizes during repeated charge and discharge, so that electrical contact between electrode materials is lost, and a solid electrolyte interface film cannot stably exist in an electrolyte solution, resulting in a reduction in cycle life and a loss in capacity. In addition, the low conductivity of silicon severely limits the full utilization of its capacity and rate capability of the silicon electrode material.
The carbon material is one of the preferred active matrixes of the silicon-based composite material, mainly because the carbon material has good conductivity and small volume change, and in addition, the carbon material has light weight and rich sources. After the silicon material is coated with carbon, the conductivity of the material can be enhanced, the agglomeration among silicon nano particles and the volume expansion of the material are reduced, and a layer of stable and smooth solid electrolyte interface film can be formed on the surface of the carbon, so that the cycle life is prolonged to a certain extent, and the rate capability is improved. At present, although the silicon/carbon composite anode material is commercially applied on a small scale, the defect that the volume expansion thereof causes the rapid decay of the material capacity is not fundamentally improved.
Disclosure of Invention
The invention aims to solve the technical problems that the silicon/carbon composite negative electrode material is modified, the volume change of silicon in the lithium intercalation/deintercalation process is reduced, the rapid capacity attenuation caused by the loss of electric contact between electrode materials due to structural collapse and pulverization in the repeated charge and discharge process is inhibited, the defect of rapid material capacity attenuation caused by the volume expansion of the silicon/carbon composite negative electrode material is overcome, and the cycle performance of the silicon/carbon composite negative electrode material is improved.
The invention provides a plant cellulose modified silicon/carbon composite anode material which comprises the following components in parts by weight: 1-3 parts of carbide of plant cellulose, 3-10 parts of silicon, 80-120 parts of graphite and 5-10 parts of pyrolytic carbon.
Preferably, the composition comprises the following components in parts by weight: 1.7 parts of plant cellulose carbide, 5 parts of silicon, 85 parts of graphite and 8.3 parts of pyrolytic carbon.
The invention also provides a preparation method of the plant cellulose modified silicon/carbon composite anode material, which comprises the following steps:
(1) preparing an ethanol solution with the volume fraction of 1-100% for later use;
(2) taking 40-100 parts by weight of high polymer, adding the ethanol solution prepared in the step (1) into the high polymer, and stirring and dissolving to obtain a high polymer solution;
(3) adding grinding balls, 3-10 parts by weight of silicon powder and the high polymer solution obtained in the step (2) into a ball milling tank, transferring a cleaning solution into the ball milling tank by using the ethanol solution container prepared in the step (1), performing ball milling dispersion for 1-10 hours, adding 5-10 parts by weight of plant cellulose, and continuing performing ball milling dispersion for 0.5-24 hours;
(4) filtering and separating the ball-liquid mixture obtained in the step (3), flushing the grinding balls by using the ethanol solution prepared in the step (1), and combining the flushing liquid with the suspension obtained by filtering;
(5) heating the suspension obtained in the step (4) to boil, then keeping the temperature at 80-120 ℃ for 20-240min, checking the concentrated solution by using a glass rod, stopping heating when a small amount of drawing wires are formed, adding 80-120 parts by weight of graphite, and continuously stirring and evaporating the solvent to obtain a viscous paste;
(6) drying the thick paste obtained in the step (5) at the temperature of 80-200 ℃ to obtain mixed powder;
(7) placing the mixed powder obtained in the step (6) in a roasting furnace, pre-blowing protective gas for 0.5-3h, then heating to 700-1400 ℃ at the speed of 2-10 ℃/min, preserving the heat for 2-10h at the temperature, and carrying out pyrolysis carbonization on the carbonizable organic matters in the mixed powder to obtain a silicon/carbon pyrolysate;
(8) and (3) crushing the silicon/carbon pyrolysate prepared in the step (7), grinding until D50 is 5-25 mu m, and sieving through a 150-mesh 200-mesh standard sieve to obtain the plant cellulose modified silicon/carbon composite negative electrode material.
Preferably, the mass ratio of the ethanol solution to the high polymer in the step (2) is the ethanol solution: high polymer 100: (4-10), the high polymer is one or more of PEG6000, PEG4000, PEG2000, PEG1000 and PEG 200.
Preferably, the plant cellulose in the step (3) has a molecular formula: (C)6H10O5) n, the diameter is 10-30 μm, the length is 100-2000 μm, and the surface porous aperture is 10-100 nm; the particle size of the silicon powder is 20-1000 nm.
Preferably, the mass ratio of the added ball materials in the step (3) is grinding ball: silicon powder (10-100): 1, the grinding balls are zirconia balls with the diameter of 2mm, and the frequency of the ball mill is 20-50 Hz.
Preferably, the concentration in the step (5) is carried out for 50-90min at the temperature of 90-100 ℃.
Preferably, the drying in the step (6) is carried out at the temperature of 80-120 ℃.
Preferably, the protective gas is pre-blown in the step (7) for 50-90min, and then the temperature is raised to 1000-.
Preferably, the graphite in the step (5) is natural graphite, artificial graphite or a commercial graphite-based lithium ion battery cathode material, and the heating and concentrating device is a water bath kettle, an oil bath kettle or an electric heating furnace; the drying equipment is a hot air circulation oven, a box-type atmosphere furnace, a muffle furnace, a tube furnace, a fluidized bed dryer or an atomization dryer; the protective gas in the step (7) is one of nitrogen, helium, neon, argon, krypton or xenon; the crushing mode adopted in the step (8) is grinding crushing, ball milling crushing, air flow crushing or rolling crushing.
The principle of the invention is as follows: the plant cellulose modified silicon/carbon composite negative electrode material takes a fiber extract in plants as an additive, and plant fibers are doped in the silicon-carbon composite material in the form of carbides with diameter fiber layer structures after carbonization. The plant cellulose and the material proportion in the material have important influence on the specific capacity and the cycle performance of the final electrode material, wherein the addition of the plant cellulose can enhance the adsorption of silicon particles on the surface of a fiber extract by utilizing the combined action of surface porosity and the compatibility of PEG, and inhibit the agglomeration of nano silicon particles, but the excessive addition of the fibers can cause the adverse effects of reduction of tap density, reduction of specific capacity, enlargement of specific surface and the like of the composite material. The plant cellulose is subjected to high-energy ball milling to form a fibrous lamellar structure with the diameter of 0.1-500 mu m, the surface of the fibrous lamellar structure is porous, rough and elastic, silicon particles with different particle sizes can be adsorbed and embedded when the fibrous lamellar structure is mixed with silicon powder and graphite powder and subjected to ball milling, the fibrous porous structure has elasticity, the volume expansion and contraction of silicon and graphite in the lithium embedding and removing processes can be absorbed, the change of interface stress can be inhibited, meanwhile, the porous fibrous lamellar structure can serve as a 'physical bridge' and a three-dimensional reticular conductive network for lithium ion and electron transmission, and in addition, the structure is favorable for inhibiting the agglomeration of silicon in the preparation process of the composite material and improving the uniformity of silicon dispersion. After high temperature treatment at 700 plus 1400 ℃, a layered and soft carbon structure after fiber carbonization is formed in the final negative electrode material, so that the conductivity of the composite material and the structural stability of the composite material in the charging and discharging process are enhanced. The wet ball milling process can improve the mixing uniformity and the nano silicon dispersion uniformity, and the proper ball milling frequency and ball milling time can ensure that the size of the plant cellulose is 0.1-500um and is beneficial to the nanocrystallization of silicon particles; drying to remove water, which is beneficial to reducing the unwanted chemical reaction side reaction in the subsequent high-temperature carbonization process; before high-temperature pyrolysis, pre-blowing protective gas for 0.5-3h aims to remove adsorbed oxygen on the surface of the material and inhibit the oxidation of the oxygen to the composite material in the high-temperature pyrolysis carbonization process, and the control of the high-temperature pyrolysis temperature aims to completely carbonize the composite material and remove impurities except for carbon and silicon.
The invention has the beneficial effects that: the invention utilizes the combined action of plant cellulose surface porosity and compatibility with PEG to enhance the adsorption of silicon particles on the surface of a fiber extract and inhibit the agglomeration of nano silicon particles, the plant cellulose is subjected to high-energy ball milling to form a fibrous lamellar structure, the fibrous carbonized lamellar and soft carbon structure is formed by high-temperature treatment, and the fibrous lamellar structure carbide is doped in a silicon-carbon composite material, so that the volume change of silicon in the lithium intercalation/deintercalation process is effectively reduced, and the structural collapse and pulverization caused by repeated charge and discharge of the silicon are inhibitedThe loss of electric contact between the pole materials leads the capacity to be rapidly attenuated, and the conductivity of the composite material and the structural stability of the composite material in the charging and discharging processes are enhanced, so that the defect of rapid attenuation of the material capacity caused by volume expansion of the silicon/carbon composite cathode material is overcome, and the cycle performance of the silicon/carbon composite cathode material is improved. In addition, the plant extract cellulose used in the present invention has the formula (C)6H10O5) And n, the raw material source is wide, the raw material source comprises plants such as bamboo, wood, straw stalk, reed stalk, wheat stalk and the like, and the raw material used as the lithium ion battery cathode material has the advantages of low cost, environmental protection, sustainable development and the like.
Drawings
FIG. 1 shows Si/G/F2SEM photographs at different magnifications;
FIG. 2 is Si/G/F2And XRD pattern of Si/G/P;
FIG. 3 is Si/G/F2First week charge and discharge curves of Si/G/P and F at 0.2C room temperature;
FIG. 4 is Si/G/F1、Si/G/F2、Si/G/F3And the cycling performance of Si/G/P at room temperature and 0.2C rate.
Detailed Description
The plant cellulose modified silicon/carbon composite negative electrode material comprises the following components in parts by weight: 1-3 parts of carbide of plant cellulose, 3-10 parts of silicon, 80-120 parts of graphite and 5-10 parts of pyrolytic carbon.
Secondly, the preparation method of the plant cellulose modified silicon/carbon composite negative electrode material comprises the following steps:
(1) preparing an ethanol solution with the volume fraction of 1-100% for later use;
(2) taking 40-100 parts by weight of high polymer, adding the ethanol solution prepared in the step (1) into the high polymer, and stirring and dissolving to obtain a high polymer solution; the mass ratio of the ethanol solution to the high polymer is ethanol solution: high polymer 100: (4-10), the high polymer is one or more of PEG6000, PEG4000, PEG2000, PEG1000 and PEG 200;
(3) adding grinding balls, 3-10 parts by weight of silicon powder and the high polymer solution obtained in the step (2) into a ball milling tank, and using the step (1)) Transferring the cleaning solution to a ball milling tank, performing ball milling dispersion for 1-10h, adding 5-10 parts by weight of plant cellulose, and continuing ball milling dispersion for 0.5-24 h; the molecular formula of the plant cellulose is as follows: (C)6H10O5) n, the diameter is 10-30 μm, the length is 100-2000 μm, and the surface porous aperture is 10-100 nm; the particle size of the silicon powder is 20-1000 nm; adding grinding balls according to the mass ratio of the added ball materials: silicon powder (10-100): 1, the grinding balls are zirconia balls with the diameter of 2mm, and the frequency of the ball mill is 20-50 Hz;
(4) filtering and separating the ball-liquid mixture obtained in the step (3), flushing the grinding balls by using the ethanol solution prepared in the step (1), and combining the flushing liquid with the suspension obtained by filtering;
(5) heating the suspension obtained in the step (4) to boil, then keeping the temperature at 80-120 ℃ for 20-240min, checking the concentrated solution by using a glass rod, stopping heating when a small amount of drawing wires are formed, adding 80-120 parts by weight of graphite, and continuously stirring and evaporating the solvent to obtain a viscous paste; the graphite is natural graphite, artificial graphite or a commercial graphite-based lithium ion battery cathode material; the heating and concentrating device is a water bath kettle or an oil bath kettle or an electric heating furnace; the drying equipment is a hot air circulation oven, a box-type atmosphere furnace, a muffle furnace, a tube furnace, a fluidized bed dryer or an atomization dryer;
(6) drying the thick paste obtained in the step (5) at the temperature of 80-200 ℃ to obtain mixed powder;
(7) placing the mixed powder obtained in the step (6) in a roasting furnace, pre-blowing protective gas for 0.5-3h, then heating to 700-1400 ℃ at the speed of 2-10 ℃/min, preserving the heat for 2-10h at the temperature, and carrying out pyrolysis carbonization on the carbonizable organic matters in the mixed powder to obtain a silicon/carbon pyrolysate; the protective gas is one of nitrogen, helium, neon, argon, krypton or xenon;
(8) crushing the silicon/carbon pyrolysate prepared in the step (7), grinding until D50 is 5-25 mu m, and sieving with a 150-200-mesh standard sieve to obtain the plant cellulose modified silicon/carbon composite anode material; the crushing mode is grinding crushing, ball milling crushing, airflow crushing or rolling crushing.
Thirdly, an electrochemical testing method:
the negative electrode material prepared by the method, the conductive agent acetylene black and the binder polyvinylidene fluoride (PVdF) are uniformly mixed according to the mass ratio of 85: 8: 7 by using N-methyl pyrrolidone (NMP) as a solvent, coated on a Cu foil, dried at 120 ℃ for 12 hours, rolled and punched into a wafer with the diameter of 12 mm. Assembling the wafer in an argon-protected MBRAUN LABstar glove box to simulate battery assembly, and assembling the wafer in an environment H2O and O2In an amount of less than 1X 10-6Using metal lithium sheet as negative electrode, Celgard2400 as separator, 1 mol.L-1LiPF-6DMC (dimethyl carbonate) + DEC (diethyl carbonate) + EC (ethylene carbonate) (DMC: DEC: EC in a volume ratio of 1: 1) as electrolyte. The test of the simulated battery adopts constant current charge and discharge, the charge and discharge current density is 0.2C (360 mA/g for 1C), and the charge and discharge voltage range is 0.003-2.0V.
Fourthly, characterizing the structure and the appearance of the material:
the surface topography of the material is observed by using an S-4800 type field emission scanning electron microscope and a scanning electron microscope of Hitachi, Japan; the samples were subjected to phase analysis using a German bruker model DiscoverD 8X-ray diffractometer (Cu Ka, tube voltage 40kV, scanning step 0.01 °, Current 40mA, scanning Range 5-90 °, scanning speed 0.02 °/0.1S) and Shimadza, Japan, XRD 7000S X-ray diffractometer (Cu Ka, tube voltage 40kV, tube Current 40mA, scanning Range 10-80 °, scanning step 0.02 °).
Example 1:
the plant cellulose modified silicon/carbon composite negative electrode material comprises the following components in parts by weight: 2.3 parts of plant cellulose carbide, 10 parts of silicon, 120 parts of graphite and 9.5 parts of pyrolytic carbon.
The preparation method of the plant cellulose modified silicon/carbon composite anode material comprises the following steps:
(1) preparing an ethanol solution with the volume fraction of 1-100% for later use;
(2) adding 100 parts by weight of high polymer into the ethanol solution prepared in the step (1), and stirring and dissolving to obtain a high polymer solution; the mass ratio of the ethanol solution to the high polymer is ethanol solution: high polymer 100: 7, the high polymer is one or more of PEG2000, PEG1000 and PEG 200;
(3) adding grinding balls, 10 parts by weight of silicon powder and the high polymer solution obtained in the step (2) into a ball milling tank, transferring a cleaning solution into the ball milling tank by using the ethanol solution container prepared in the step (1), performing ball milling dispersion for 8-10h, adding 10 parts by weight of plant cellulose, and continuing performing ball milling dispersion for 0.5-12 h; the molecular formula of the plant cellulose is as follows: (C)6H10O5) n, the diameter is 10-30 μm, the length is 100-2000 μm, and the surface porous aperture is 10-100 nm; the particle size of the silicon powder is 20-1000 nm; adding grinding balls according to the mass ratio of the added ball materials: silicon powder is 100: 1, the grinding balls are zirconia balls with the diameter of 2mm, and the frequency of the ball mill is 20-30 Hz;
(4) filtering and separating the ball-liquid mixture obtained in the step (3), flushing the grinding balls by using the ethanol solution prepared in the step (1), and combining the flushing liquid with the suspension obtained by filtering;
(5) heating the suspension obtained in the step (4) to boil, then keeping the temperature at 80-90 ℃ for concentrating for 180-;
(6) drying the thick paste obtained in the step (5) at the temperature range of 170-200 ℃ to obtain mixed powder;
(7) placing the mixed powder obtained in the step (6) in a roasting furnace, pre-blowing protective gas for 2.5-3h, then heating to 1200-1400 ℃ at the speed of 10 ℃/min, preserving the heat for 3-6h at the temperature, and carrying out pyrolysis carbonization on the carbonizable organic matters in the mixed powder to obtain a silicon/carbon pyrolysate;
(8) crushing the silicon/carbon pyrolysate prepared in the step (7), grinding the crushed silicon/carbon pyrolysate until the D50 is 5-25 mu m, and sieving the crushed silicon/carbon pyrolysate with a 150-mesh 200-mesh standard sieve to obtain the plant cellulose modified silicon/carbon composite anode material Si/G/F1。
The plant cellulose modified silicon/carbon composite negative material obtained in the embodimentPolar material Si/G/F1Under the conditions of room temperature and 0.2 multiplying power, the first-cycle charging capacity is 465mAh/g, the first-cycle efficiency is 90 percent, and the specific capacity after 100-cycle circulation is 138 mAh/g.
Example 2:
the plant cellulose modified silicon/carbon composite negative electrode material comprises the following components in parts by weight: 1.7 parts of plant cellulose carbide, 5 parts of silicon, 85 parts of graphite and 8.3 parts of pyrolytic carbon.
The preparation method of the plant cellulose modified silicon/carbon composite anode material comprises the following steps:
(1) preparing an ethanol solution with the volume fraction of 1-100% for later use;
(2) taking 80 parts by weight of high polymer, adding the ethanol solution prepared in the step (1) into the high polymer, and stirring and dissolving to obtain a high polymer solution; the mass ratio of the ethanol solution to the high polymer is ethanol solution: high polymer 100: 10, the high polymer is PEG 4000;
(3) adding grinding balls, 5 parts by weight of silicon powder and the high polymer solution obtained in the step (2) into a ball milling tank, transferring a cleaning solution into the ball milling tank by using the ethanol solution container prepared in the step (1), performing ball milling dispersion for 5 hours, adding 7.5 parts by weight of plant cellulose, and continuing performing ball milling dispersion for 12 hours; the molecular formula of the plant cellulose is as follows: (C)6H10O5) n, the diameter is 10-30 μm, the length is 100-2000 μm, and the surface porous aperture is 10-100 nm; the particle size of the silicon powder is 20-1000 nm; adding grinding balls according to the mass ratio of the added ball materials: silicon powder is 50: 1, the grinding balls are zirconia balls with the diameter of 2mm, and the frequency of the ball mill is 30-40 Hz;
(4) filtering and separating the ball-liquid mixture obtained in the step (3), flushing the grinding balls by using the ethanol solution prepared in the step (1), and combining the flushing liquid with the suspension obtained by filtering;
(5) heating the suspension obtained in the step (4) to boil, then keeping the temperature at 90-100 ℃ and concentrating for 50-90min, checking the concentrated solution with a glass rod, stopping heating when a small amount of the suspension is in a wiredrawing shape, adding 85 parts by weight of graphite, and continuously stirring and evaporating the solvent to obtain a viscous paste;
(6) drying the thick paste obtained in the step (5) at the temperature of 80-120 ℃ to obtain mixed powder;
(7) placing the mixed powder obtained in the step (6) in a roasting furnace, pre-blowing protective gas for 50-90min, heating to 1000-;
(8) crushing the silicon/carbon pyrolysate prepared in the step (7), grinding the crushed silicon/carbon pyrolysate until the D50 is 5-25 mu m, and sieving the crushed silicon/carbon pyrolysate with a 150-mesh 200-mesh standard sieve to obtain the plant cellulose modified silicon/carbon composite anode material Si/G/F2。
The plant cellulose modified silicon/carbon composite anode material Si/G/F obtained in the embodiment2Under the conditions of room temperature and 0.2 multiplying power, the first discharge capacity 472 is mAh/g, the first efficiency is 90 percent, and the specific capacity after circulation for 100 weeks is 349 mAh/g.
Example 3:
the plant cellulose modified silicon/carbon composite negative electrode material comprises the following components in parts by weight: 1.2 parts of plant cellulose carbide, 3 parts of silicon, 100 parts of graphite and 5.0 parts of pyrolytic carbon.
The preparation method of the plant cellulose modified silicon/carbon composite anode material comprises the following steps:
(1) preparing an ethanol solution with the volume fraction of 1-100% for later use;
(2) taking 40 parts by weight of high polymer, adding the ethanol solution prepared in the step (1) into the high polymer, and stirring and dissolving to obtain a high polymer solution; the mass ratio of the ethanol solution to the high polymer is ethanol solution: high polymer 100: 4, the high polymer is PEG 4000;
(3) adding grinding balls, 3 parts by weight of silicon powder and the high polymer solution obtained in the step (2) into a ball milling tank, transferring a cleaning solution into the ball milling tank by using the ethanol solution container prepared in the step (1), performing ball milling dispersion for 1-3h, adding 5 parts by weight of plant cellulose, and continuing performing ball milling dispersion for 20-24 h; the molecular formula of the plant cellulose is as follows: (C)6H10O5) n, the diameter is 10-30 μm, the length is 100-2000 μm, and the surface porous aperture is 10-100 nm;the particle size of the silicon powder is 20-1000 nm; adding grinding balls according to the mass ratio of the added ball materials: silicon powder is 10: 1, the grinding balls are zirconia balls with the diameter of 2mm, and the frequency of the ball mill is 40-50 Hz;
(4) filtering and separating the ball-liquid mixture obtained in the step (3), flushing the grinding balls by using the ethanol solution prepared in the step (1), and combining the flushing liquid with the suspension obtained by filtering;
(5) heating the suspension obtained in the step (4) to boil, then keeping the temperature at the temperature of 100-;
(6) drying the thick paste obtained in the step (5) at the temperature of 80-100 ℃ to obtain mixed powder;
(7) placing the mixed powder obtained in the step (6) in a roasting furnace, pre-blowing protective gas for 1-2h, then heating to 700-;
(8) crushing the silicon/carbon pyrolysate prepared in the step (7), grinding the crushed silicon/carbon pyrolysate until the D50 is 5-25 mu m, and sieving the crushed silicon/carbon pyrolysate with a 150-mesh 200-mesh standard sieve to obtain the plant cellulose modified silicon/carbon composite anode material Si/G/F3。
The plant cellulose modified silicon/carbon composite anode material Si/G/F obtained in the embodiment3The first discharge capacity is 460mAh/g under the conditions of room temperature and 0.2 multiplying power, the first efficiency is 90 percent, and the specific capacity after circulation for 100 weeks is 143 mAh/g.
Example 4:
this example is a comparative test of example 2, and compared with example 2, the present example has the same raw material ratio and preparation process, except that no plant cellulose is added in example 4, and a silicon/carbon composite anode material is prepared.
The silicon/carbon composite anode material comprises the following components in parts by weight: 5 parts of silicon, 85 parts of graphite and 8.3 parts of pyrolytic carbon.
The preparation method of the silicon/carbon composite anode material of the embodiment comprises the following steps:
(2) preparing an ethanol solution with the volume fraction of 1-100% for later use;
(2) taking 80 parts by weight of high polymer, adding the ethanol solution prepared in the step (1) into the high polymer, and stirring and dissolving to obtain a high polymer solution; the mass ratio of the ethanol solution to the high polymer is ethanol solution: high polymer 100: 10, the high polymer is PEG 4000;
(3) adding grinding balls, 5 parts by weight of silicon powder and the high polymer solution obtained in the step (2) into a ball milling tank, transferring a cleaning solution into the ball milling tank by using the ethanol solution container prepared in the step (1), and continuing ball milling and dispersing for 12 hours after ball milling and dispersing for 5 hours; the molecular formula of the plant cellulose is as follows: (C)6H10O5) n, the diameter is 10-30 μm, the length is 100-2000 μm, and the surface porous aperture is 10-100 nm; the particle size of the silicon powder is 20-1000 nm; adding grinding balls according to the mass ratio of the added ball materials: silicon powder is 50: 1, the grinding balls are zirconia balls with the diameter of 2mm, and the frequency of the ball mill is 30-40 Hz;
(4) filtering and separating the ball-liquid mixture obtained in the step (3), flushing the grinding balls by using the ethanol solution prepared in the step (1), and combining the flushing liquid with the suspension obtained by filtering;
(5) heating the suspension obtained in the step (4) to boil, then keeping the temperature at 90-100 ℃ and concentrating for 50-90min, checking the concentrated solution with a glass rod, stopping heating when a small amount of the suspension is in a wiredrawing shape, adding 85 parts by weight of graphite, and continuously stirring and evaporating the solvent to obtain a viscous paste;
(6) drying the thick paste obtained in the step (5) at the temperature of 80-120 ℃ to obtain mixed powder;
(7) placing the mixed powder obtained in the step (6) in a roasting furnace, pre-blowing protective gas for 50-90min, heating to 1000-;
(8) and (3) crushing the silicon/carbon pyrolysate prepared in the step (7), grinding until D50 is 5-25 mu m, and sieving through a 150-mesh 200-mesh standard sieve to obtain the plant cellulose modified silicon/carbon composite anode material Si/G/P.
The silicon/carbon composite anode material Si/G/P obtained in the embodiment has the first discharge capacity of 480mAh/G under the conditions of room temperature and 0.2 multiplying power, the first efficiency of 88 percent, and the specific capacity of 49.65mAh/G after circulation for 100 weeks
TABLE 1 description of sample number, composition and electrical properties in the examples
Example 1 Example 2 Example 3 Example 4
Sample numbering Si/G/F1 Si/G/F2 Si/G/F3 Si/G/P
Content of plant fiber before carbonization (parts by weight) 10 7.5 5 0
Content of carbonized plant fiber (parts by weight) 2.3 1.7 1.2 0
Graphite content (parts by weight) 120 85 100 85
Content of pyrolytic carbon (parts by weight) 9.5 8.3 5.0 8.3
Content of silica fume (parts by weight) 10 5 3 5
First week charge capacity (mAh/g) 465 472 460 480
First efficiency (%) 90 90 90 88
Capacity (mAh/g) for 100 cycles 138 349 143 49.65
Si/G/F in Table 11、Si/G/F2、Si/G/F3And Si/G/P respectively refers to the lithium ion battery negative electrode materials synthesized when the addition amount of the plant cellulose is 10%, 7.5%, 5% and 0%. As can be seen from Table 1, the plant cellulose modified silicon/carbon composite anode materials Si/G/F of examples 1 to 31-3The specific capacities after the cycling for 100 weeks under the conditions of room temperature and 0.2 multiplying power are 138mAh/G, 349mAh/G and 143mAh/G respectively, and the specific capacity after the cycling for 100 weeks under the same conditions of the silicon/carbon composite anode material Si/G/P of the embodiment 4 is 49.65 mAh/G. In example 4, compared with example 2, the raw material ratio and the preparation process are the same, except that no plant cellulose is added in example 4, but the capacity of the silicon/carbon composite anode material obtained in example 4 after Si/G/P cycling for 100 times is far lower than that of the plant cellulose modified silicon/carbon composite anode material Si/G/F obtained in example 22. Therefore, the plant cellulose modified silicon/carbon composite negative electrode material provided by the invention can greatly improve the cycle performance of the silicon/carbon composite negative electrode material by adding the plant cellulose.
FIG. 1 is Si/G/F2SEM photographs at 10000, 40000 and 2000 times of scanning electron microscope. From A1The figure shows that the cellulose film has silicon attached to it and is distributed in the interstices of the large graphite particles, A2The figure shows that the size of the fiber sheet layer is 200-600nm, A3The graph shows that the particle size of the graphite is 15-20um, the surface of the graphite is wrapped with a layer of net, the net mainly comprises amorphous carbon and nano silicon, and the fiber carbide plays a role in establishing a conductive network. In conclusion, the sheet structure of the cellulose after sintering has an inhibition effect on the aggregation of silicon and plays a role in establishing a conductive network.
FIG. 2 is Si/G/F2XRD diffraction patterns of the sample and the Si/G/P sample. It can be seen that 2 theta at 26.1 deg., 43.9 deg., 54.1 deg., and 77.8 deg. respectively is a stoneTypical characteristic peaks corresponding to crystal faces of ink (002) (110) (004) (110) are consistent with JCPDS cards 75-1621, and indicate that the material has a graphite component; 2 theta is positioned at 28.6 degrees and 47.4 degrees, and is a characteristic diffraction peak corresponding to a (111) (220) crystal face of silicon, which is consistent with JCPDS cards 27-1402, so that the crystalline silicon component exists, the two groups of patterns are basically consistent, the addition of fiber carbide does not change the crystal phase structure of the composite, and the fiber sheet layer and the carbide of high polymer are both amorphous carbon structures.
FIG. 3 is Si/G/F2First week charge and discharge curves at 0.2C room temperature of Si/G/P and F, wherein F is a plant cellulose carbide. As can be seen from FIG. 3, the first-week discharge capacity of F is only 220mAh/G, and the first-week charge-discharge performance is far inferior to that of Si/G/P, but Si/G/F is obtained by modifying Si/G/P with F, and the first-week discharge capacity of Si/G/F is the same as that of Si/G/P, but the cycle performance of Si/G/F is far superior to that of Si/G/P.
FIG. 4 is Si/G/F1、Si/G/F2、Si/G/F3And the cycling performance of Si/G/P at room temperature and 0.2C rate. As can be seen from fig. 4, the addition of the plant cellulose can improve the cycle performance of the silicon/carbon composite anode material, the plant cellulose and the material proportion in the material have an important influence on the specific capacity and the cycle performance of the final electrode material, and the cycle performance of the material is influenced by too much or too little addition of the plant cellulose.

Claims (10)

1. The plant cellulose modified silicon/carbon composite negative electrode material is characterized by comprising the following components in parts by weight: 1-3 parts of plant cellulose carbide, 3-10 parts of silicon, 80-120 parts of graphite and 5-10 parts of pyrolytic carbon, wherein the plant cellulose modified silicon/carbon composite negative electrode material is prepared by the following steps:
(1) preparing an ethanol solution with the volume fraction of 1-100% for later use;
(2) taking 40-100 parts by weight of high polymer, adding the ethanol solution prepared in the step (1) into the high polymer, and stirring and dissolving to obtain a high polymer solution;
(3) adding grinding balls, 3-10 parts by weight of silicon powder and the high polymer solution obtained in the step (2) into a ball milling tank, washing a container by using the ethanol solution prepared in the step (1), transferring a washing solution into the ball milling tank, performing ball milling dispersion for 1-10 hours, adding 5-10 parts by weight of plant cellulose, and continuing performing ball milling dispersion for 0.5-24 hours;
(4) filtering and separating the ball-liquid mixture obtained in the step (3), flushing the grinding balls by using the ethanol solution prepared in the step (1), and combining the flushing liquid with the suspension obtained by filtering;
(5) heating the suspension obtained in the step (4) to boil, then keeping the temperature at 80-120 ℃ for 20-240min, checking the concentrated solution by using a glass rod, stopping heating when a small amount of drawing wires are formed, adding 80-120 parts by weight of graphite, and continuously stirring and evaporating the solvent to obtain a viscous paste;
(6) drying the thick paste obtained in the step (5) at the temperature of 80-200 ℃ to obtain mixed powder;
(7) placing the mixed powder obtained in the step (6) in a roasting furnace, pre-blowing protective gas for 0.5-3h, then heating to 700-1400 ℃ at the speed of 2-10 ℃/min, preserving the heat for 2-10h at the temperature, and carrying out pyrolysis carbonization on the carbonizable organic matters in the mixed powder to obtain a silicon/carbon pyrolysate;
(8) and (3) crushing the silicon/carbon pyrolysate prepared in the step (7), grinding until D50 is 5-25 mu m, and sieving through a 150-mesh 200-mesh standard sieve to obtain the plant cellulose modified silicon/carbon composite negative electrode material.
2. The plant cellulose modified silicon/carbon composite anode material as claimed in claim 1, which comprises the following components in parts by weight: 1.7 parts of plant cellulose carbide, 5 parts of silicon, 85 parts of graphite and 8.3 parts of pyrolytic carbon.
3. The preparation method of the plant cellulose modified silicon/carbon composite anode material as claimed in claim 1, characterized by comprising the following steps:
(1) preparing an ethanol solution with the volume fraction of 1-100% for later use;
(2) taking 40-100 parts by weight of high polymer, adding the ethanol solution prepared in the step (1) into the high polymer, and stirring and dissolving to obtain a high polymer solution;
(3) adding grinding balls, 3-10 parts by weight of silicon powder and the high polymer solution obtained in the step (2) into a ball milling tank, washing a container by using the ethanol solution prepared in the step (1), transferring a washing solution into the ball milling tank, performing ball milling dispersion for 1-10 hours, adding 5-10 parts by weight of plant cellulose, and continuing performing ball milling dispersion for 0.5-24 hours;
(4) filtering and separating the ball-liquid mixture obtained in the step (3), flushing the grinding balls by using the ethanol solution prepared in the step (1), and combining the flushing liquid with the suspension obtained by filtering;
(5) heating the suspension obtained in the step (4) to boil, then keeping the temperature at 80-120 ℃ for 20-240min, checking the concentrated solution by using a glass rod, stopping heating when a small amount of drawing wires are formed, adding 80-120 parts by weight of graphite, and continuously stirring and evaporating the solvent to obtain a viscous paste;
(6) drying the thick paste obtained in the step (5) at the temperature of 80-200 ℃ to obtain mixed powder;
(7) placing the mixed powder obtained in the step (6) in a roasting furnace, pre-blowing protective gas for 0.5-3h, then heating to 700-1400 ℃ at the speed of 2-10 ℃/min, preserving the heat for 2-10h at the temperature, and carrying out pyrolysis carbonization on the carbonizable organic matters in the mixed powder to obtain a silicon/carbon pyrolysate;
(8) and (3) crushing the silicon/carbon pyrolysate prepared in the step (7), grinding until D50 is 5-25 mu m, and sieving through a 150-mesh 200-mesh standard sieve to obtain the plant cellulose modified silicon/carbon composite negative electrode material.
4. The preparation method of the plant cellulose modified silicon/carbon composite anode material as claimed in claim 3, wherein the mass ratio of the ethanol solution to the high polymer in the step (2) is ethanol solution: high polymer 100: (4-10), the high polymer is one or more of PEG6000, PEG4000, PEG2000, PEG1000 and PEG 200.
5. The method for preparing the plant cellulose modified silicon/carbon composite anode material as claimed in claim 3, wherein the molecular formula of the plant cellulose in the step (3) is as follows: (C)6H10O5) n, diameter10-30 μm, 100-2000 μm long, and 10-100nm porous pore diameter on the surface; the particle size of the silicon powder is 20-1000 nm.
6. The preparation method of the plant cellulose modified silicon/carbon composite anode material as claimed in claim 3, wherein the mass ratio of the added ball material in the step (3) is grinding ball: silicon powder (10-100): 1, the grinding balls are zirconia balls with the diameter of 2mm, and the frequency of the ball mill is 20-50 Hz.
7. The preparation method of the plant cellulose modified silicon/carbon composite anode material as claimed in claim 3, wherein the concentration in the step (5) is maintained at 90-100 ℃ for 50-90 min.
8. The method for preparing the plant cellulose modified silicon/carbon composite anode material as claimed in claim 3, wherein the drying in the step (6) is carried out at a temperature ranging from 80 ℃ to 120 ℃.
9. The method for preparing the plant cellulose modified silicon/carbon composite anode material as claimed in claim 3, wherein the protective gas is pre-blown in the step (7) for 50-90min, and then the temperature is raised to 1000-1200 ℃ at the rate of 5 ℃/min, and the temperature is maintained at the temperature for 3-10 h.
10. The preparation method of the plant cellulose modified silicon/carbon composite anode material as claimed in claim 3, wherein the graphite in the step (5) is natural graphite, artificial graphite or a commercial graphite-based lithium ion battery anode material, and the heating and concentrating device is a water bath kettle or an oil bath kettle or an electric heating furnace; the drying equipment is a hot air circulation oven, a box-type atmosphere furnace, a muffle furnace, a tube furnace, a fluidized bed dryer or an atomization dryer; the protective gas in the step (7) is one of nitrogen, helium, neon, argon, krypton or xenon; the crushing mode adopted in the step (8) is grinding crushing, ball milling crushing, air flow crushing or rolling crushing.
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