CN113206249A - Lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance and preparation method thereof - Google Patents

Lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance and preparation method thereof Download PDF

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CN113206249A
CN113206249A CN202110421855.1A CN202110421855A CN113206249A CN 113206249 A CN113206249 A CN 113206249A CN 202110421855 A CN202110421855 A CN 202110421855A CN 113206249 A CN113206249 A CN 113206249A
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silicon
carbon
solid electrolyte
carbon nano
oxygen composite
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CN113206249B (en
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蔡新辉
胡博
徐梓炜
刘锐剑
金海侹
吕猛
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Huzhou Qiyuan Jincan New Energy Technology Co ltd
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a lithium battery, and discloses a lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance and a preparation method thereof. In addition, the solid electrolyte is introduced, so that lithium ion migration of lithium ions at an interface can be improved, and side reaction at the interface is reduced, and the multiplying power and the cycle performance of the silicon-oxygen composite negative electrode material are taken into consideration.

Description

Lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance and preparation method thereof
Technical Field
The invention relates to the field of lithium batteries, in particular to a lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance and a preparation method thereof.
Background
In recent years, with the widespread use of portable electronic devices and the increasing popularity of electric vehicles, the energy density of conventional carbon cathode materials is far from meeting the requirements of the existing markets. The silica negative electrode material is widely researched due to the fact that the silica negative electrode material has higher theoretical specific capacity (2680mAh/g), but the silica negative electrode material still has problems in application in the field of lithium battery negative electrodes:
1) the volume expansion of the silicon-oxygen negative electrode material can reach 200% in the charging and discharging processes, and the particle structure is easy to damage, so that the uncontrollable growth of an SEI film on the surface of the particle is caused. At the moment, the interface between the silicon-oxygen cathode material and the electrolyte can generate more side reactions and consume the electrolyte, so that the high electron ion transmission resistance remarkably influences the cycle and rate performance;
2) the electronic conductivity and the ionic conductivity of the silicon-oxygen cathode material are low, so that the electrochemical properties of the pure silicon-oxygen cathode material, such as first efficiency, cycle, multiplying power and the like, are poor.
In the existing research on silicon-oxygen composite negative electrode materials, methods for solving the problems of volume expansion and pulverization and low conductivity of the silicon-oxygen composite negative electrode materials mainly comprise reducing the particle size and coating an amorphous conductive carbon layer. However, the single reduction of the particle size tends to result in a larger contact area between the silica particles and the electrolyte, and the electrolyte is more easily consumed during the charge and discharge processes. The coated amorphous carbon layer can improve the electronic conductivity and relieve the particle crushing problem, and still has the defects of loss of electric contact among particles after cyclic expansion, limited improvement of the ionic conductivity and the like.
Disclosure of Invention
The invention provides a lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance and a preparation method thereof, aiming at solving the technical problems of volume expansion and pulverization, low electron conductivity and low ionic conductivity of the existing silicon-oxygen negative electrode material. The silicon oxide composite negative electrode material takes the silicon oxide with carbon nano materials and solid electrolyte (two forms) distributed on the surface as an inner core, a layer of amorphous carbon is coated outside the inner core, the amorphous carbon coating can relieve the expansion and pulverization of silicon oxide particles in the charging and discharging processes of the material, and forms a conductive framework with the carbon nano materials, so that the electronic conductivity and the ionic conductivity are high, and the problem of electric contact failure caused in the process of repeatedly inserting and extracting lithium is solved. In addition, the solid electrolyte is introduced, so that lithium ion migration of lithium ions at an interface can be improved, and side reaction at the interface is reduced, and the multiplying power and the cycle performance of the silicon-oxygen composite negative electrode material are taken into consideration.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance, which takes silicon monoxide with carbon nano materials and solid electrolyte distributed on the surface as an inner core, and takes amorphous carbon coated on the surface of the silicon monoxide as a coating layer; the carbon nano material and the solid electrolyte are distributed on the surface of the silicon oxide in a dispersed form or in a form of the carbon nano material modified solid electrolyte; wherein the proportion of the silicon oxide is 70-98wt%, the proportion of the carbon nano material is 0.01-5%, the proportion of the solid electrolyte is 0.01-10%, and the proportion of the amorphous carbon is 1-15%. The silicon-oxygen composite negative electrode material is unique in structural design, the carbon nano material and the solid electrolyte are introduced on the basis of coating the silicon oxide particles with the amorphous carbon, and the carbon nano material and the solid electrolyte are firmly and uniformly combined on the surfaces of the silicon oxide particles through the chemical bond action of the amorphous carbon coating, so that the problems of particle pulverization, low electronic conductivity and low ionic conductivity of the silicon-oxygen material can be solved. The limiting effect of the amorphous carbon coating layer can avoid the structural pulverization failure problem caused by lithium intercalation and deintercalation of silica particles, the carbon nano material and the amorphous carbon can form a conductive framework, the electronic transmission problem among particles and between particles and a current collector can be solved by the synergistic effect, and the electrical contact failure caused in the process of repeatedly lithium intercalation and deintercalation is avoided. The combined action of the solid electrolyte and the amorphous carbon can obviously improve the interface stability of the silicon-oxygen cathode and the electrolyte, reduce the side reaction of the lithium ion intercalation and deintercalation with the interface of the electrolyte, and avoid the problems of too fast consumption and gas generation of the electrolyte, thereby enabling the material to have excellent rate capability and cycle performance at the same time.
The lithium ion conductivity of the ceramic solid electrolyte such as LLZO, LLZTO and the like is as high as 1-4～10-3S cm-1Ion conductivity of nearly commercial liquid electrolyte 10-3S cm-1The surface of the silicon-oxygen negative electrode is coated with solid electrolytes such as LLZTO, LLZO and the like, and can act synergistically with an amorphous carbon layer and a carbon nano material to form an artificial SEI film coating layer with high lithium ion conductivity and high mechanical stability, and the coating layer improves the coulombic efficiency and the cycle stability of the silicon-oxygen negative electrode by weakening the decomposition of an electrolyte. In addition, the excellent lithium ion transmission capability of the coating layer can obviously improve the rate capability of the silicon-oxygen negative electrode.
Further, the carbon nanomaterial and the solid electrolyte can be distributed on the surface of the silicon oxide in the form of the carbon nanomaterial-modified solid electrolyte. The carbon nano materials such as graphene and carbon nano tubes have ultrahigh electronic conductivity, the carbon nano materials are used for modifying the solid electrolyte, the modified solid electrolyte which simultaneously considers ionic conductivity and electronic conductivity can be obtained, and compared with the condition that the carbon nano materials and the solid electrolyte are distributed on the surface of the silicon oxide in a dispersed mode, the modified solid electrolyte mainly has the following advantages: 1) solid electrolyte particles are uniformly loaded by a liquid phase modification process and the advantage of large surface area of the carbon nano material, so that the phenomenon that a large amount of nano-scale solid electrolyte particles are agglomerated and the advantage of ultrahigh ionic conductivity of the solid electrolyte cannot be exerted can be avoided; 2) when the solid electrolyte is dispersed on the surface of the silicon oxide in a dispersion mode, the solid electrolyte is easy to fall off and lose efficacy due to the volume effect of the silicon-oxygen cathode particles during charging and discharging, and the problem of falling off of the solid electrolyte can be solved by loading the solid electrolyte on the surface of the carbon nano material through pre-modification; 3) the modified solid electrolyte can coordinate with a carbon nano material, has ultrahigh electronic conductivity and lithium ion conductivity, and is better favorable for improving the coulombic efficiency, the cycle stability and the rate capability of a silica-oxygen cathode.
Preferably, the solid electrolyte is Li7-xLa3TaxZr2-xO12(LLZTO) and/or LiLa3Zr2O12(LLZO)；x＝0-2。
Preferably, the silicon monoxide is bulk particles, the amorphous carbon is soft carbon or hard carbon, and the carbon nano material is in a sheet or tubular structure.
Sheet or tubular carbon nano materials such as graphene and carbon nano tubes are introduced into the cathode material, the long-range ordered structure of the carbon nano materials can be cooperated with the amorphous carbon coating layer, a conductive network is constructed on the surfaces of particles and electrodes, and the problem of low silica conductivity is solved.
Preferably, the silica has a silicon to oxygen ratio of 1 to 1.08:1 and particles having a median diameter of 0.5 to 10 μm.
Preferably, the carbon nanomaterial is one of a carbon nanotube and graphene.
In a second aspect, the invention provides a preparation method of a silicon-oxygen composite anode material, which comprises two schemes:
for the carbon nano-material and the solid electrolyte distributed on the surface of the silicon oxide in a dispersed form, the preparation method comprises the following steps:
1) mixing and dispersing the silica powder, the carbon nano-material slurry, the solid electrolyte powder and the solvent uniformly, and then performing ultrasonic dispersion to obtain uniform slurry;
2) drying, granulating and depolymerizing the uniform slurry to obtain powder particles;
3) carrying out solid-phase or liquid-phase coating treatment on the powder particles by adopting a carbon source, and cooling to obtain a precursor;
4) and transferring the precursor into carbonization equipment, heating to 600-1200 ℃ in a protective atmosphere, preserving the heat for 2-24h, cooling, taking out, and screening to obtain the silicon-oxygen composite anode material.
According to the scheme, the solid electrolyte, the silica powder and the carbon nano material are dispersed and ultrasonically treated to form a uniform mixture, after drying and granulation, carbon source coating is carried out through a solid phase or a liquid phase, and amorphous carbon is formed through carbonization, so that the silica composite negative electrode material is finally obtained.
The carbon nanomaterial modified solid electrolyte is distributed on the surface of the silicon oxide in a form of carbon nanomaterial modified solid electrolyte, and the preparation method comprises the following steps:
1) mixing and dispersing the carbon nano-material slurry, the solid electrolyte powder and the solvent uniformly, and then performing ultrasonic dispersion to obtain uniform slurry;
2) drying, granulating and depolymerizing the uniform slurry, and performing heat treatment at the temperature of 250-350 ℃ for 1-3h to obtain a carbon nano material modified solid electrolyte;
3) uniformly mixing the obtained carbon nano material modified solid electrolyte and the silica fume to obtain powder particles, then carrying out solid-phase or liquid-phase coating treatment by adopting a carbon source, and cooling to obtain a precursor;
4) and transferring the precursor into carbonization equipment, heating to 600-1200 ℃ in a protective atmosphere, preserving the heat for 2-24h, cooling, taking out, and screening to obtain the silicon-oxygen composite anode material.
In the scheme, the solid electrolyte and the carbon nano material are dispersed and ultrasonically treated to form a uniform mixture, the carbon nano material modified solid electrolyte is obtained after drying, granulation and depolymerization and low-temperature heat treatment, carbon source coating is carried out through a solid phase or a liquid phase, and amorphous carbon is formed through carbonization to finally obtain the silicon-oxygen composite negative electrode material.
Preferably, in step 1), the carbon nanomaterial slurry contains a thickener; the thickening agent is one or more of sodium carboxymethylcellulose, polytetrafluoroethylene, polyacrylic acid and polyvinylidene fluoride; the solvent is one or more of isopropanol, deionized water, N-methyl pyrrolidone, ethanol and glycol; the ultrasonic dispersion time is 0.2-1 h.
Preferably, in step 2), the drying and granulating method is vacuum drying, freeze drying or spray drying. The depolymerization mode is one or more of rolling mill, mechanical mill, jet mill and ball mill. The low-temperature heat treatment equipment is a vertical kettle or a heating VC mixer.
Preferably, in the step 3), the carbon source is at least one of pitch, resin and tar; further the softening point of the asphalt is 100-300 ℃; the resin is one or more of phenolic resin, acrylonitrile resin, furan resin and polyoxyethylene resin; the tar is one or more of phenol oil, washing oil and anthracene oil.
Preferably, in the step 3), the ratio of the carbon source to the ground particles is 3-25: 100. If the carbon source proportion is too high, the capacity of the composite material is low, and if the carbon source proportion is too low, the first effect of the material is low.
Preferably, the solid phase or liquid phase coating is realized by one or more of a roller furnace, a vertical kettle, a mechanical fusion machine and a heating VC mixer.
Preferably, in the step 4), the carbonization equipment is a box-type carbonization furnace, a roller kiln, a tubular carbonization furnace or a pushed slab kiln.
Compared with the prior art, the invention has the beneficial effects that: the negative electrode material disclosed by the invention is unique in structural design, and an artificial SEI film coating layer with high lithium ion conductivity and high mechanical stability is formed by coating amorphous carbon, a carbon nano material and a solid electrolyte (two distribution forms) on the surface of a silicon monoxide particle.
Drawings
Fig. 1 is XRD patterns of the silicon oxygen composite anode materials prepared in example one (upper curve) and comparative example one (lower curve).
Fig. 2 is an SEM picture of the silicon-oxygen composite negative electrode material prepared in the first example.
Fig. 3 is a comparative graph of charging cycle curves of the silicon-oxygen composite negative electrode materials prepared in the first embodiment, the second embodiment and the first comparative embodiment.
Fig. 4 is a comparison of the full electrical cycle curves of the silicon-oxygen composite negative electrode material prepared in example one (upper curve), example two (middle curve) and comparative example one (lower curve) and the artificial graphite compound sample.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance takes silicon monoxide with carbon nanometer materials and solid electrolyte distributed on the surface as an inner core, and takes amorphous carbon coated on the surface of the silicon monoxide as a coating layer; the carbon nano material and the solid electrolyte are distributed on the surface of the silicon oxide in a dispersed form or in a form of the carbon nano material modified solid electrolyte; wherein the proportion of the silicon oxide is 70-98wt%, the proportion of the carbon nano material is 0.01-5%, the proportion of the solid electrolyte is 0.01-10%, and the proportion of the amorphous carbon is 1-15%. Wherein the silicon monoxide is massive particles, the silicon-oxygen ratio is 1-1.08:1, and the median diameter of the particles is 0.5-10 μm. The amorphous carbon is soft carbon or hard carbon, and the solid electrolyte is Li7-xLa3TaxZr2-xO12(LLZTO) and/or Li7La3Zr2O12(LLZO); x is 0-2. The carbon nanomaterial is of a sheet or tubular structure, and is preferably one of a carbon nanotube and graphene.
A preparation method of a silicon-oxygen composite anode material comprises two schemes:
for the carbon nano-material and the solid electrolyte distributed on the surface of the silicon oxide in a dispersed form, the preparation method comprises the following steps:
1) mixing and dispersing the silica powder, the carbon nano-material slurry, the solid electrolyte powder and the solvent uniformly, and then performing ultrasonic dispersion for 0.2-1h to obtain uniform slurry. Wherein the carbon nano-material slurry contains a thickening agent; the thickening agent is one or more of sodium carboxymethylcellulose, polytetrafluoroethylene, polyacrylic acid and polyvinylidene fluoride; the solvent is one or more of isopropanol, deionized water, N-methyl pyrrolidone, ethanol and ethylene glycol.
2) And drying and granulating (vacuum drying, freeze drying or spray drying) the uniform slurry, depolymerizing (one or more of rolling mill, mechanical mill, jet mill and ball mill), and depolymerizing to obtain powder particles.
3) And (2) carrying out solid-phase or liquid-phase coating treatment on the powder particles by adopting a carbon source through one or more of a roller furnace, a vertical kettle, a mechanical fusion machine and a heating VC mixer according to the mass ratio of 3-25: 100, and cooling to obtain a precursor. The carbon source is at least one of asphalt, resin and tar; further the softening point of the asphalt is 100-300 ℃; the resin is one or more of phenolic resin, acrylonitrile resin, furan resin and polyoxyethylene resin; the tar is one or more of phenol oil, washing oil and anthracene oil.
4) And transferring the precursor into carbonization equipment (a box-type carbonization furnace, a roller kiln, a tubular carbonization furnace or a pushed slab kiln), heating to 600-1200 ℃ in a protective atmosphere, preserving the heat for 2-24h, cooling, taking out, and screening to obtain the silica composite anode material.
The carbon nanomaterial modified solid electrolyte is distributed on the surface of the silicon oxide in a form of carbon nanomaterial modified solid electrolyte, and the preparation method comprises the following steps:
1) mixing and dispersing the carbon nano-material slurry, the solid electrolyte powder and the solvent uniformly, and then performing ultrasonic dispersion for 0.2-1h to obtain uniform slurry; wherein the carbon nano-material slurry contains a thickening agent; the thickening agent is one or more of sodium carboxymethylcellulose, polytetrafluoroethylene, polyacrylic acid and polyvinylidene fluoride; the solvent is one or more of isopropanol, deionized water, N-methyl pyrrolidone, ethanol and ethylene glycol.
2) And drying and granulating (vacuum drying, freeze drying or spray drying) the uniform slurry, depolymerizing (one or more of rolling mill, mechanical mill, jet mill and ball mill), performing heat treatment at the temperature of 250-350 ℃ for 1-3h, and performing heat treatment (a vertical kettle or a heating VC mixer) to obtain the modified solid electrolyte of the carbon nano material.
3) And modifying the obtained carbon nano material, uniformly mixing the modified carbon nano material with a solid electrolyte and silica fume to obtain powder particles, performing solid-phase or liquid-phase coating treatment on a carbon source through one or more of a roller furnace, a vertical kettle, a mechanical fusion machine and a heating VC mixer (the mass ratio of the powder particles to the carbon source is 3-25: 100), and cooling to obtain a precursor. The carbon source is at least one of asphalt, resin and tar; further the softening point of the asphalt is 100-300 ℃; the resin is one or more of phenolic resin, acrylonitrile resin, furan resin and polyoxyethylene resin; the tar is one or more of phenol oil, washing oil and anthracene oil.
4) And transferring the precursor into carbonization equipment (a box-type carbonization furnace, a roller kiln, a tubular carbonization furnace or a pushed slab kiln), heating to 600-1200 ℃ in a protective atmosphere, preserving the heat for 2-24h, cooling, taking out, and screening to obtain the silica composite anode material.
EXAMPLE one (distribution on the surface of a silica in the form of a carbon nanomaterial-modified solid electrolyte)
0.2kg of graphene slurry (solid content 5%, solvent NMP) and 0.05kg of solid electrolyte (Li)6.9La3Ta0.1Zr1.9O12200nm) and 1.5kg of isopropanol are added into a 5L dispersing and sanding machine, uniform slurry is obtained after high-speed dispersion for 2 hours, and an ultrasonic generator is inserted into the slurry for ultrasonic treatment for 1 hour. And (3) carrying out spray drying granulation on the slurry to obtain a solid mixture, carrying out jet milling on the depolymerized material, transferring the depolymerized material into a heating VC mixer, and carrying out heat treatment at 300 ℃ for 2 hours to obtain the graphene modified solid electrolyte. Mixing the obtained modified solid electrolyte, 1.88kg of silicon monoxide powder (SiO, the median particle size of 5 microns) and 0.1kg of petroleum asphalt (softening point at 200 ℃) for 1 hour by using a three-dimensional mixer, then transferring the mixture into an experimental roller furnace, carrying out solid phase coating treatment, mixing and heating to 550 ℃ under protective atmosphere, preserving heat for 2 hours, and naturally cooling to obtain a precursor. And transferring the precursor material into a roller kiln, heating to 1050 ℃ in a nitrogen atmosphere, carbonizing for 20 hours, and keeping the temperature for 5 hours. Naturally cooling, and sieving with a 250-mesh sieve to obtain the silicon-oxygen composite negative electrode material.
Homogenizing the prepared silicon-oxygen composite negative electrode material, carbon black, CMC and SBR according to the proportion of 94.5: 1.5: 2.0, coating and rolling to prepare a working electrode, taking a lithium sheet as a counter electrode to prepare a button cell, carrying out charge-discharge test, and taking lithium cobaltate as a positive electrode to carry out full cell test.
Example two (carbon nanomaterial and solid electrolyte dispersed form distributed on the silica surface)
0.2kg of graphene slurry (solid content 5%, solvent NMP) and 0.05kg of solid electrolyte (Li)6.9La3Ta0.1Zr1.9O12200nm), 1.88kg of silica powder (SiO, with a median particle size of 5 μm) and 1.5kg of isopropanol were added into a 5L dispersing and sanding machine, and dispersed at high speed for 2 hours to obtain a uniform slurry, and an ultrasonic generator was inserted into the slurry and subjected to ultrasonic treatment for 1 hour. And (3) carrying out spray drying granulation on the slurry to obtain a solid mixture, and carrying out depolymerization by an air flow mill to obtain powder particles. Transferring the powder particles obtained by depolymerization and 0.1kg of petroleum asphalt (softening point at 200 ℃) into an experimental roller furnace, carrying out solid phase coating treatment, mixing and heating to 550 ℃ under protective atmosphere, preserving heat for 2h, and naturally cooling to obtain a precursor. And transferring the precursor material into a roller kiln, heating to 1050 ℃ in a nitrogen atmosphere, carbonizing for 20 hours, and keeping the temperature for 5 hours. Naturally cooling, and sieving with a 250-mesh sieve to obtain the silicon-oxygen composite negative electrode material.
Homogenizing the prepared silicon-oxygen composite negative electrode material, carbon black, CMC and SBR according to the proportion of 94.5: 1.5: 2.0, coating and rolling to prepare a working electrode, taking a lithium sheet as a counter electrode to prepare a button cell, carrying out charge-discharge test, and taking lithium cobaltate as a positive electrode to carry out full cell test.
Tests prove that the reversible discharge specific capacity of the silicon-oxygen composite negative electrode material reaches 1295.8mAh/g, the first efficiency is 80.1%, and the reversible capacity of 1171.1mAh/g is still available after 50 weeks of circulation.
EXAMPLE III
0.8kg of carbon nanotube slurry (solid content 1%, solvent NMP) and 0.5kg of solid electrolyte (Li)6.8La3Ta0.2Zr1.8O12500nm), 15.0kg of silica powder (SiO, with a median particle size of 4 μm) and 10kg of isopropanol were added into a 30L dispersion sand mill, and dispersed at high speed for 2 hours to obtain a uniform slurry, and an ultrasonic generator was inserted into the slurry and subjected to ultrasonic treatment for 2 hours. Mixing the pulpThe material is transferred into an electric heating constant temperature drying oven to be dried at 90 ℃, and then is ground and graded by a mechanical mill to obtain powder particles. . And transferring the obtained powder particles and lkg phenolic oil into a mechanical fusion machine, and carrying out low-temperature liquid-phase coating treatment to obtain a precursor. And transferring the precursor material into a roller kiln, heating to 1050 ℃ in a nitrogen atmosphere, and carbonizing for 24 hours and 6 hours in total. Naturally cooling, and sieving with a 250-mesh sieve to obtain the silicon-oxygen composite negative electrode material.
Through tests, the reversible discharge specific capacity of the silicon-oxygen composite negative electrode material reaches 1328.9mAh/g, the first efficiency is 79.6%, and the reversible capacity of 1139.1mAh/g is still available after 50 weeks of circulation.
Example four
0.5kg of carbon nanotube slurry (solid content 1%, solvent NMP) and 0.02kg of solid electrolyte (Li)6.9La3Ta0.1Zr1.9O12500nm), 2kg of silica powder (SiO, with a median particle size of 4 μm) and 2kg of NMP were added into a 5L dispersion sand mill, and dispersed at high speed for 2 hours to obtain a uniform slurry, and an ultrasonic generator was inserted into the slurry and subjected to ultrasonic treatment for 0.5 hour. And transferring the slurry into an electric heating constant-temperature drying box or a muffle furnace for drying at 90 ℃, and then crushing and grading by using an air flow mill to obtain powder particles. And transferring the obtained powder particles, 0.3kg of petroleum asphalt and 0.5kg of anthracene oil into a mechanical fusion machine, performing low-temperature liquid phase coating treatment, transferring the material into VC thermal compounding equipment, and keeping the temperature at 500 ℃ for 2 hours to obtain a precursor. And transferring the precursor material into a roller kiln, heating to 1000 ℃ in a nitrogen atmosphere, carbonizing for 18 hours in total, and preserving heat for 5 hours. Naturally cooling, and sieving with a 250-mesh sieve to obtain the silicon-oxygen composite negative electrode material.
Tests prove that the reversible discharge specific capacity of the silicon-oxygen composite negative electrode material reaches 1226.0mAh/g, the first efficiency is 80.1%, and the reversible capacity of 1071.7mAh/g is still available after 50 weeks of circulation.
Comparative example one (without solid electrolyte)
Transferring 1.88kg of silicon monoxide powder (with the median particle size of 5 microns) and 0.1kg of petroleum asphalt (with the softening point of 200 ℃) into VC thermal compounding equipment, carrying out solid phase coating treatment, mixing and heating to 550 ℃ under a protective atmosphere, preserving heat for 2 hours, and naturally cooling to obtain a precursor. And transferring the precursor material into a roller kiln, heating to 1050 ℃ in a nitrogen atmosphere, carbonizing for 20 hours, and keeping the temperature for 5 hours. Naturally cooling, and sieving with a 250-mesh sieve to obtain the silicon-oxygen composite negative electrode material.
Through tests, the reversible capacity of the single-coating amorphous carbon silicon oxygen composite negative electrode material also reaches 1299.0mAh/g, the first efficiency is 77.8%, but the half cell has only 788.0mAh/g reversible capacity after being cycled for 50 weeks at 0.1C/0.1C.
Comparison of Performance
(1) The difference between the first embodiment and the second embodiment is only the combination form of the carbon nanomaterial and the solid electrolyte; while comparative example one differs in that no solid electrolyte was added. FIG. 1 is XRD patterns of silicon-oxygen composite anode materials prepared in example one and comparative example one, and it can be seen from the XRD patterns that the silicon-oxygen composite anode materials are successfully prepared in example one, no obvious impurity peak is generated, and SiO can be observedxThe typical diffraction peak of LLZTO, and the (002) crystal plane peak of carbon can be observed at 26.8 degrees, which indicates the existence of amorphous carbon coating layer on the surface. No diffraction peak of LLZTO was observed in the XRD pattern of comparative example one. The morphology is shown in SEM of figure 2, the lamellar graphene material is modified by solid electrolyte nano particles, and the solid electrolyte nano particles are compounded on the surfaces of silicon oxygen particles or filled between the silicon oxygen particles, so that an excellent conductive network can be constructed when the electrode is manufactured.
(2) The physical property test and the electrochemical test of the silicon-oxygen composite anode material prepared in the first embodiment and the second embodiment and the first embodiment are as follows:
Figure BDA0003027480880000081
as can be seen from the comparative plot of charging cycle in FIG. 3 and the data in the above table, the silicon-oxygen composite negative electrode material prepared in the first example, which is 0.5% graphene, 2.5% LLZTO, and 5% carbon source coating ratio of pitch with softening point at 200 deg.C, D507.21 mu m, the specific surface area is 2.97m2/g, the reversible capacity of the composite material reaches 1282.7mAh/g, the first efficiency is 80.3 percent, and the button cell still has 1203.2mAh/g after being cycled for 50 weeks at 0.1C/0.1CThe reversible capacity and the capacity retention rate of 93.8% are superior to those of the second example. The electric performance can be further improved by modifying the solid electrolyte in advance by using the graphene. The second example is superior to the first comparative example, which shows that the introduction of the solid electrolyte can significantly improve the electrical properties.
(3) Mixing the obtained silica composite negative electrode material with artificial graphite to obtain a silicon-carbon negative electrode material with the capacity of 450mAh/g, and manufacturing a soft package full battery, wherein the test results of the full battery are as follows:
Figure BDA0003027480880000082
as can be seen from fig. 4 and the above table, the retention rate of the silicon-carbon anode material obtained by the compounding in the embodiment is still 91.2% after the silicon-carbon anode material is cycled for 300 weeks at 1C/1C, the percentage of the 4C charging constant current section is 65.2%, and the retention rate of the 4C discharge capacity is 76.3%. All performance indexes are better than those of the mixed sample of the second embodiment and the first comparative example. The comparison of the three shows that the multiplying power and the cycle performance of the silica composite cathode material obtained by pre-modifying the solid electrolyte by adopting the carbon nano material and then coating the amorphous carbon are obviously improved.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. The utility model provides a lithium cell silicon oxygen composite negative electrode material with good electrochemistry performance which characterized in that: taking the silicon monoxide with the surface distributed with carbon nano materials and solid electrolyte as an inner core, and taking amorphous carbon coated on the surface of the silicon monoxide as a coating layer; the carbon nano material and the solid electrolyte are distributed on the surface of the silicon oxide in a dispersed form or in a form of the carbon nano material modified solid electrolyte; wherein the proportion of the silicon oxide is 70-98wt%, the proportion of the carbon nano material is 0.01-5%, the proportion of the solid electrolyte is 0.01-10%, and the proportion of the amorphous carbon is 1-15%.
2. The silicon-oxygen composite anode material according to claim 1, wherein the solid electrolyte is Li7- xLa3TaxZr2-xO12And/or LiLa3Zr2O12；x=0-2。
3. The silicon-oxygen composite anode material as claimed in claim 1, wherein the silicon monoxide is bulk particles, the amorphous carbon is soft carbon or hard carbon, and the carbon nanomaterial is of a sheet-like or tubular structure.
4. The silicon oxygen composite anode material according to claim 3, wherein the silicon oxide has a silicon to oxygen ratio of 1 to 1.08:1, and the median particle diameter of the particles is 0.5 to 10 μm.
5. The silicon-oxygen composite anode material of claim 1, wherein the carbon nanomaterial is one of carbon nanotubes and graphene.
6. A method for preparing the silicon-oxygen composite negative electrode material as claimed in any one of claims 1 to 5, wherein:
for the carbon nano material and the solid electrolyte distributed on the surface of the silicon oxide in a dispersed mode, the preparation method of the silicon-oxygen composite negative electrode material comprises the following steps:
1) mixing and dispersing the silica powder, the carbon nano-material slurry, the solid electrolyte powder and the solvent uniformly, and then performing ultrasonic dispersion to obtain uniform slurry;
2) drying, granulating and depolymerizing the uniform slurry to obtain powder particles;
3) carrying out solid-phase or liquid-phase coating treatment on the powder particles by adopting a carbon source, and cooling to obtain a precursor;
4) transferring the precursor into carbonization equipment, heating to 600-1200 ℃ in a protective atmosphere, preserving heat for 2-24h, cooling, taking out, and screening to obtain a silicon-oxygen composite anode material;
the carbon nanomaterial modified solid electrolyte is distributed on the surface of the silicon oxide, and the preparation method of the silicon-oxygen composite negative electrode material comprises the following steps:
1) mixing and dispersing the carbon nano-material slurry, the solid electrolyte powder and the solvent uniformly, and then performing ultrasonic dispersion to obtain uniform slurry;
2) drying, granulating and depolymerizing the uniform slurry, and performing heat treatment at the temperature of 250-350 ℃ for 1-3h to obtain a carbon nano material modified solid electrolyte;
3) uniformly mixing the obtained carbon nano material modified solid electrolyte and the silica fume to obtain powder particles, then carrying out solid-phase or liquid-phase coating treatment by adopting a carbon source, and cooling to obtain a precursor;
4) and transferring the precursor into carbonization equipment, heating to 600-1200 ℃ in a protective atmosphere, preserving the heat for 2-24h, cooling, taking out, and screening to obtain the silicon-oxygen composite anode material.
7. The method according to claim 6, wherein, in step 1),
the carbon nano-material slurry contains a thickening agent; the thickening agent is one or more of sodium carboxymethylcellulose, polytetrafluoroethylene, polyacrylic acid and polyvinylidene fluoride;
the solvent is one or more of isopropanol, deionized water, N-methyl pyrrolidone, ethanol and glycol;
the ultrasonic dispersion time is 0.2-1 h.
8. The method according to claim 6, wherein in step 2),
the drying and granulating method is vacuum drying, freeze drying or spray drying;
the depolymerization mode is one or more of rolling mill, mechanical mill, jet mill and ball mill;
the low-temperature heat treatment equipment is a vertical kettle or a heating VC mixer.
9. The method according to claim 6, wherein, in step 3),
the carbon source is at least one of asphalt, resin and tar;
the softening point of the asphalt is 100-300 ℃;
the resin is one or more of phenolic resin, acrylonitrile resin, furan resin and polyoxyethylene resin;
the tar is one or more of phenol oil, washing oil and anthracene oil;
the ratio of the carbon source to the powder particles is 3-25: 100;
the solid phase or liquid phase coating is realized by one or more of a roller furnace, a vertical kettle, a mechanical fusion machine and a heating VC mixer.
10. The method according to claim 6, wherein in the step 4), the carbonizing apparatus is a box-type carbonizing furnace, a roller kiln, a tubular carbonizing furnace, or a pushed slab kiln.
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