CN111653746A - Silicon monoxide negative electrode material and preparation method and application thereof - Google Patents

Silicon monoxide negative electrode material and preparation method and application thereof Download PDF

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CN111653746A
CN111653746A CN202010489504.XA CN202010489504A CN111653746A CN 111653746 A CN111653746 A CN 111653746A CN 202010489504 A CN202010489504 A CN 202010489504A CN 111653746 A CN111653746 A CN 111653746A
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negative electrode
electrode material
carbon
conductive carbon
silicon oxide
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林少雄
陆大班
赵宇飞
王辉
辛昱
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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Abstract

The invention provides a silicon monoxide negative electrode material and a preparation method and application thereof. The silicon monoxide negative electrode material has a core-shell structure, wherein the inner core is composed of nano silicon monoxide, conductive carbon and amorphous carbon, and the outer part of the core is wrapped by a polymer-conductive carbon layer; the nano-silicon oxide and the conductive carbon in the inner core are dispersed in the amorphous carbon; wherein, the mass content of the conductive carbon is 1-5%, and the mass content of the amorphous carbon is 10-20%. The invention also provides a preparation method of the anode material. When the silicon oxide negative electrode material is used as a negative electrode of a lithium ion battery, the silicon oxide negative electrode material has higher conductivity and better cycle performance.

Description

Silicon monoxide negative electrode material and preparation method and application thereof
Technical Field
The invention relates to a negative electrode material, in particular to a silicon monoxide negative electrode material, and belongs to the technical field of lithium ion batteries.
Background
Silicon-based anode materials are considered as one of the alternative products of the existing commercial carbon anode materials, but cannot be commercialized due to the large volume effect in the charge and discharge processes, so that a great deal of modification research is performed by researchers. Based on two aspects of theoretical research and experimental research, the research progress of the silicon-based anode material is summarized, and the research on the novel alloy anode material is expected to be promoted.
In recent years, rapid development in the field of new energy power generation puts new requirements on matched energy storage systems. In the updating and upgrading of energy storage batteries, lithium ion batteries have become an important research field due to various advantages of the lithium ion batteries, and have been practically applied to a large number of energy storage projects to achieve certain results.
The capacity of the lithium ion battery is determined by active lithium ions of a positive electrode material and the lithium-inserting and extracting capacity of a negative electrode material, and the stability of the positive electrode and the negative electrode in various environments determines the performance of the battery and even seriously affects the safety of the battery, so that the performance of the electrode determines the comprehensive performance of the lithium ion battery to a certain extent.
However, the current commercial lithium ion battery cathode material is mainly graphite carbon cathode material, and the theoretical specific capacity is only 372mAh/g (LiC)6) Further development of lithium ion batteries is severely limited. The silicon-based material is a research system with the highest theoretical specific capacity in the negative electrode material, and the formed alloy is LixSi (x ═ 0-4.4), with theoretical specific capacities up to 4200mAh/g, is considered as a replacement for carbon anode materials due to its low intercalation potential, low atomic mass, high energy density and high Li mole fraction in Li-Si alloysA substitute product.
However, silicon anode materials have not, in time, been able to be used commercially in a wide range of applications because, while having many advantages, silicon anode materials also have several disadvantages. Firstly, the silicon negative electrode material undergoes volume change of more than 300% in the charging and discharging processes, such high volume expansion and shrinkage easily leads to the pulverization of the electrode material, the separation of the electrode material from the contact with the current collector and the electrode conductive network, and the volume change brings about the generation of new surfaces, so that a new solid-electrolyte interface (SEI) needs to be formed, thereby leading to the large consumption of the electrolyte and further leading to the substantial reduction of the cycle life. On the other hand, the electrical conductivity and lithium ion diffusion speed of silicon are lower than those of graphite, which limits the performance of silicon under high-current and high-power conditions.
The material mainly utilizes the gaps among graphite to embed nano silicon. Graphite, being relatively "soft" can greatly buffer the expansion of silicon particles, and the first active lithium ions consumed is primarily required to generate SEI, so its coulombic efficiency is also in a marginally acceptable range. However, in order to buffer the expansion of nano-silicon and graphite, the compaction density of the material is relatively low, which results in the reduction of the volume energy density of the cell. More seriously, because the expansion of silicon is more than 300%, and the normal graphite expansion is about 10%, after the composite material expands and contracts during charging and discharging, the graphite is difficult to restore to the original state (namely the graphite and the silicon are converted from the initial surface contact into point contact), so that the nano silicon loses electric contact and is deactivated, which is one of the reasons that the cycle decay of the silicon-carbon material is fast.
At present, the mainstream commercial silicon oxide composite negative electrode material is generally coated with carbon, so that the conductivity of the material is improved, meanwhile, the silicon oxide negative electrode material is prevented from being directly contacted with electrolyte, and the cycle performance of the material is improved.
The large-scale application of the silicon-based negative electrode material still faces a lot of tests, the cycle performance and expansion of the material are further improved, the production cost is reduced, and the majority of scientific researchers and manufacturers still pay great attention.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a silica negative electrode material having a higher conductivity and a lower volume expansion.
The invention also aims to provide a preparation method of the silicon monoxide negative electrode material.
In order to achieve the technical purpose, the invention provides a silicon monoxide negative electrode material which has a core-shell structure, wherein the inner part (core) is composed of nano silicon monoxide, conductive carbon and amorphous carbon, and the outer part (shell) is wrapped by a polymer-conductive carbon layer; the nano-silicon oxide and the conductive carbon in the inner core are dispersed in the amorphous carbon; wherein the total mass of the nano-silicon oxide, the conductive carbon and the amorphous carbon in the nano-silicon oxide is 100%, the mass content of the conductive carbon is 1% -5%, and the mass content of the amorphous carbon is 10% -20%.
The silicon oxide negative electrode material has a relatively perfect spherical or sphere-like core-shell structure, the inner core is formed by secondary granulation of nano silicon oxide, conductive carbon and amorphous carbon, and the surface shell is formed by polymer-conductive carbon with certain elasticity and conductivity. The cores of the silicon oxide negative electrode material are physically connected through the conductive carbon inside the secondary particles, so that the silicon oxide negative electrode material has higher conductivity; the expansion effect is further improved by the buffer expansion of the secondary particles of the inner core and the double buffer expansion of the surface core.
In one embodiment of the invention, the average particle size D50 of the silica negative electrode material is 5 μm to 7 μm, wherein the outer polymer-conductive carbon layer has a thickness of 5nm to 50 nm.
In one embodiment of the invention, the nano-silica used has an average particle size D50 of 50nm to 120 nm; preferably 80nm to 100 nm.
In one embodiment of the present invention, the conductive carbon used is at least one of carbon nanotubes, superconducting carbon black, acetylene black, and ketjen carbon, and is preferably a carbon nanotube. The amorphous carbon used may be at least one of soft carbon or hard carbon; preferably, the amorphous carbon is at least one of the following: citric acid, glucose, cellulose, sucrose, sugars, sugar polymers, polysaccharides, polyimides, polyacrylonitrile, polystyrene, polydivinylbenzene, polyvinylpyridine, polypyrrole, polythiophene, polyaniline, and copolymers of citric acid, glucose, cellulose, sucrose, sugars, sugar polymers, polysaccharides, polyimides, polyacrylonitrile, polystyrene, polydivinylbenzene, polyvinylpyridine, polypyrrole, polythiophene, polyaniline.
In one embodiment of the present invention, the conductive carbon content in the polymer-conductive carbon layer is 1% to 10% by mass based on 100% by mass of the total mass of the polymer-conductive carbon layer. In one embodiment of the invention, the polymer employed is a polymerization of at least one of the following: dimethylacrylamide, aniline, thiophene, pyrrole, polydimethylsiloxane, methyl methacrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, acrylamide, maleic anhydride, sodium p-vinylbenzene sulfonate, sodium allyl sulfonate, vinyl acetate, isooctyl acrylate and functional group-containing perfluoropolyether.
The invention also provides a preparation method of the silicon monoxide negative electrode material, which comprises the following steps:
adding conductive carbon and amorphous carbon into nano-silicon oxide, mixing, performing spray drying for secondary granulation, and performing high-temperature sintering carbonization to obtain a first mixture;
uniformly dispersing conductive carbon in a polymer solution to obtain a second mixture;
and dispersing the first mixture into the second mixture, stirring, adding an oxidant for in-situ polymerization, filtering the obtained material, cleaning and drying to obtain the silicon monoxide negative electrode material.
In one embodiment of the invention, the temperature of the high-temperature sintering carbonization is 600 ℃ to 800 ℃ for 3 hours when the mixture is prepared.
In one embodiment of the present invention, the first mixture is dispersed in the second mixture, and the stirring time is generally 0.5h to 2 h; oxidizing double bonds of the polymer by adding an oxidant to promote reaction, wherein the oxidant can be selected from ammonium persulfate, potassium persulfate, ferric chloride, hydrogen peroxide and bromine water; the molar ratio of polymer to oxidant is 1: 1-1: 4.
the invention also provides a lithium ion battery which comprises a component formed by the silicon oxide negative electrode material. Including, but not limited to, anodes formed from the above-described silica anode materials of the present invention.
According to the silicon oxide negative electrode material, the nanoscale silicon oxide material can avoid particle fracture and pulverization caused by severe volume expansion in the lithium desorption and insertion process; the conductive carbon can greatly improve the rapid migration of ions and electrons in the material; the structure of the secondary particles (the structure of the granulated nano-silicon monoxide, conductive carbon and amorphous carbon is the secondary particles) and the amorphous carbon can expand the volume of the buffer material to a greater extent; the polymer-conductive carbon coating can further buffer the volume expansion of the material and ensure the conductivity, and is particularly suitable for being applied to lithium ion batteries.
The preparation method of the silicon monoxide negative electrode material has the advantages of low production cost, high production safety, convenient operation and easy large-scale mass production and use.
The silicon oxide negative electrode material has higher conductivity, better cycle performance and lower expansion rate through a specific structure.
Drawings
Fig. 1 is a schematic structural diagram of a silicon oxide negative electrode material according to an embodiment of the invention.
FIG. 2a is a surface topography of a silicon oxide negative electrode material according to an embodiment of the present invention.
FIG. 2b is a surface topography of a silicon oxide negative electrode material according to an embodiment of the present invention.
FIG. 2c is a surface topography of a silicon oxide negative electrode material according to an embodiment of the present invention.
FIG. 3 is a comparison of the cycling curves at room temperature for a commercial silicon oxide negative electrode material (comparative example 1) and a silicon oxide negative electrode material (example 1) in an embodiment of the present invention.
Fig. 4 is a graph comparing the cell normal temperature cycling coulombic efficiencies of the functionalized silica negative electrode material (example 1) and the commercial silica negative electrode material (comparative example 1) of one embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides a silicon oxide negative electrode material which is obtained by the following preparation method.
The silicon raw material is nodular-milled by a sand mill until the average particle size D50 is 80nm, 440g of nano-silicon oxide is added into 333g (solid content is 3%) of multi-walled carbon nanotube aqueous solution and 357g of glucose (residual carbon content is about 14%), and 120g of deionized water is added. Fully dissolving and dispersing, then carrying out spray drying, then discharging coke at 400 ℃, and then sintering and carbonizing at 700 ℃ to obtain a material with D50 of about 7 microns, thus obtaining a first mixture.
100mL of 0.1mol/L aniline monomer was dissolved in 0.5mol/L H2SO4And adding 1 wt% of multi-wall carbon nano tubes into the solution, and uniformly dispersing to obtain a second mixture.
And dispersing the first mixture in the second mixture, soaking for 7h, and precooling to 0 ℃ to obtain a mixed solution.
3g of ammonium persulfate was dissolved in 300mL of H having a molar concentration of 0.5mol/L2SO4In the solution, precooled to 0 ℃ to obtain an initiating solution.
And then dropwise adding the initiating solution into the mixed solution in an ice-water bath, carrying out polymerization reaction for 6 hours at the temperature of 0 ℃, filtering, repeatedly washing for three times by using deionized water, and drying in an oven to obtain the silicon monoxide negative electrode material.
The negative electrode material of silicon oxide of this example had a structure as shown in fig. 1, and the average particle size D50 of the negative electrode material of silicon oxide was about 7 μm.
Fig. 2a, 2b, and 2c are surface topography diagrams of the silica negative electrode material of the present embodiment, and as can be seen from fig. 2a, 2b, and 2c, after the spray drying and the polymer coating, the surface of the material is more regular, mainly spherical or spheroidal, and more favorable for buffering expansion compared with the commercially available silica material; and the edges and corners are few, so the corresponding side reactions on the surface are less, and the long-term charge-discharge cycle is facilitated.
Example 2
The embodiment provides a silicon oxide negative electrode material which is obtained by the following preparation method.
Nodular graphite is made from silicon raw materials by using a sand mill until the average particle size D50 is 50 nanometers, 37.5g of nano-silicon monoxide is added into 2.5g of superconducting black and 435g of citric acid (the residual carbon content is about 2.3%), 45g of deionized water is added, spray drying is carried out after full dissolution and dispersion, then the mixture is coked out at 400 ℃, and is sintered and carbonized at 800 ℃ to obtain a material with D50 of about 5 micrometers, so that a first mixture is obtained.
10mL of 0.1mol/L pyrrole monomer was dissolved in 0.5mol/L H2SO4Adding 10 wt% of Ketjen black into the solution, and uniformly dispersing to obtain a second mixture.
And dispersing the first mixture in the second mixture, soaking for 7h, and precooling to 0 ℃ to obtain a mixed solution.
0.2g of ferric chloride was dissolved in 30ml of H having a molar concentration of 0.5mol/L2SO4In the solution, precooled to 0 ℃ to obtain an initiating solution.
And then dropwise adding the initiating solution into the mixed solution in an ice-water bath, carrying out polymerization reaction for 6 hours at the temperature of 0 ℃, filtering, repeatedly washing for three times by using deionized water, and drying in an oven to obtain the silicon monoxide negative electrode material.
The negative electrode material of silicon oxide of this example had a structure as shown in fig. 1, and the average particle size D50 of the negative electrode material of silicon oxide was about 5 μm. The thickness of the coating layer is small, and it is considered that the difference is not large from that before coating.
Example 3
The embodiment provides a silicon oxide negative electrode material which is obtained by the following preparation method.
Nodular graphite is made from silicon raw materials by using a sand mill until the average particle size D50 is 100 nanometers, 82g of nano-silicon monoxide is taken and added with 3g of Ketjen black and 65g of cane sugar (the residual carbon content is about 23%), 100g of deionized water is added, spray drying is carried out after full dissolution and dispersion, then after decoking at 400 ℃, sintering carbonization at 1150 ℃ is carried out, and a material with D50 of about 7 micrometers is obtained, thus obtaining a first mixture.
20mL of 0.1mol/L pyrrole monomer was dissolved in 0.5mol/L H2SO4And adding 3 wt% of acetylene black into the solution, and uniformly dispersing to obtain a second mixture.
And dispersing the first mixture in the second mixture, soaking for 7h, and precooling to 0 ℃ to obtain a mixed solution.
0.1g of hydrogen peroxide was dissolved in 30ml of H having a molar concentration of 0.5mol/l2SO4In the solution, precooled to 0 ℃ to obtain an initiating solution.
And then dropwise adding the initiating solution into the mixed solution in an ice-water bath, carrying out polymerization reaction for 6 hours at the temperature of 0 ℃, filtering, repeatedly washing for three times by using deionized water, and drying in an oven to obtain the silicon monoxide negative electrode material.
The negative electrode material of silicon oxide of this example had a structure as shown in fig. 1, and the average particle size D50 of the negative electrode material of silicon oxide was about 7 μm.
Example 4
The embodiment provides a silicon oxide negative electrode material which is obtained by the following preparation method.
The silicon raw material was spheroidal graphite-treated with a sand mill until the average particle size D50 was 80nm, 435g of this nano-sized silica was added to 15g of acetylene black, and 588g of phenol resin (residual carbon amount: about 8.5%), and 212g of deionized water was added. Fully dissolving and dispersing, then carrying out spray drying, then discharging coke at 400 ℃, and then sintering and carbonizing at 800 ℃ to obtain a material with D50 of about 7 microns, thus obtaining a first mixture.
100ml of 0.1mol/L pyrrole monomer is dissolved in 0.5mol/L H2SO4And adding 3 wt% of multi-wall carbon nano tubes into the solution, and uniformly dispersing to obtain a second mixture.
And dispersing the first mixture in the second mixture, soaking for 7h, and precooling to 0 ℃ to obtain a mixed solution.
3g of ammonium persulfate were dissolved in 300ml of H having a molar concentration of 0.5mol/l2SO4In the solution, precooled to 0 ℃ to obtain an initiating solution.
And then dropwise adding the initiating solution into the mixed solution in an ice-water bath, carrying out polymerization reaction for 6 hours at the temperature of 0 ℃, filtering, repeatedly washing for three times by using deionized water, and drying in an oven to obtain the silicon monoxide negative electrode material.
The negative electrode material of silica of this example had a structure as shown in fig. 1, and the average particle size D50 of the negative electrode material of silica was about 7 μm.
Application example
Mixing the negative electrode material with commercially available graphite according to the gram volume of 600mAh/g, and mixing with sodium carboxymethylcellulose (CMC) and polyacrylic acid (PAA) according to the weight ratio of 96: 2: and 2, performing dispersed pulping, and assembling the lithium ion battery after battery cell procedures such as coating, rolling, slitting and the like, and performing corresponding tests.
After mixing a commercially available silicon negative electrode material (comparative example 1) with commercially available graphite in a gram volume of 600mAh/g, the mixture was mixed with sodium carboxymethylcellulose (CMC), polyacrylic acid (PAA), and conductive carbon black (SP) in a ratio of 94: 2: 2: and 2, performing dispersed pulping, and assembling the lithium ion battery after battery cell procedures such as coating, rolling, slitting and the like, and performing corresponding tests.
Fig. 3 is a graph comparing the normal temperature cycle curves of the battery of the functionalized silicon negative electrode material (example 1) and the commercial silicon negative electrode material (comparative example 1) of the present invention. Fig. 3 shows that the improvement of the normal temperature cycle performance of the silicon negative electrode material of the present invention is obvious. The method is mainly characterized in that the attenuation of the initial circulation capacity is obviously improved, and the later circulation trend is also improved to a certain extent.
FIG. 4 is a graph showing the comparison of the normal temperature cycling coulombic efficiencies of the batteries of the functionalized silicon oxide negative electrode material (example 1) of the present invention and the commercial silicon oxide negative electrode material (comparative example 1) blended with graphite (both negative electrode gram capacities are 600 mAh/g). It can be seen that the difference in coulombic efficiency of the inventive siliconoxide anode material is mainly reflected in that the fluctuation of coulombic efficiency is small at the initial stage of the cycle, but the coulombic efficiency is also maintained at 100% compared with the commercial silicon anode material. It is shown that the inventive silica negative electrode material is stable in the initial period of the cycle. In contrast, commercial silicon oxide negative electrode materials fluctuate widely during the early cycle, indicating that they change continuously during lithium deintercalation, i.e., they make electrical contact well or well during material expansion and contraction.
The improvement of the structural design of the silicon oxide material by the present invention can be obviously reflected by combining fig. 3 and fig. 4, and the problems of the electrical conductivity and the expansion and contraction are improved to a certain extent, so that the material losing the electrical contact due to the expansion of the material at the initial stage of the cycle is obviously reduced, the coulombic efficiency is relatively stable, and the cycle performance is obviously improved.

Claims (10)

1. The silicon monoxide negative electrode material has a core-shell structure, wherein the inner core of the silicon monoxide negative electrode material is composed of nano silicon monoxide, conductive carbon and amorphous carbon, and the outer part of the silicon monoxide negative electrode material is wrapped by a polymer-conductive carbon layer; the nano-silicon oxide and the conductive carbon in the inner core are dispersed in the amorphous carbon; wherein the total mass of the nano-silicon oxide, the conductive carbon and the amorphous carbon in the nano-silicon oxide is 100%, the mass content of the conductive carbon is 1% -5%, and the mass content of the amorphous carbon is 10% -20%.
2. The silicon oxide negative electrode material according to claim 1, wherein the conductive carbon content in the polymer-conductive carbon layer is 1% to 10% by mass based on 100% by mass of the total polymer-conductive carbon layer.
3. The negative electrode material of claim 1, wherein the negative electrode material has an average particle size D50 of 5 μm to 7 μm and the outer polymer-conductive carbon layer has a thickness of 5nm to 50 nm.
4. The negative electrode material of claim 1, wherein the average particle size D50 of the nano-sized silica particles is 50nm to 120 nm;
preferably 80nm to 100 nm.
5. The silica negative electrode material according to claim 1, wherein the conductive carbon is at least one of carbon nanotubes, superconducting carbon black, acetylene black, and ketjen carbon.
6. The negative electrode material of claim 1, wherein the amorphous carbon is at least one of soft carbon or hard carbon;
preferably, the amorphous carbon is at least one of the following: citric acid, glucose, cellulose, sucrose, sugars, sugar polymers, polysaccharides, polyimides, polyacrylonitrile, polystyrene, polydivinylbenzene, polyvinylpyridine, polypyrrole, polythiophene, polyaniline, and copolymers of citric acid, glucose, cellulose, sucrose, sugars, sugar polymers, polysaccharides, polyimides, polyacrylonitrile, polystyrene, polydivinylbenzene, polyvinylpyridine, polypyrrole, polythiophene, polyaniline.
7. The negative silica electrode material of claim 1, wherein the polymer is a polymerization of at least one of: dimethylacrylamide, aniline, thiophene, pyrrole, polydimethylsiloxane, methyl methacrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, acrylamide, maleic anhydride, sodium p-vinylbenzene sulfonate, sodium allyl sulfonate, vinyl acetate, isooctyl acrylate and functional group-containing perfluoropolyether.
8. The method for producing a silica negative electrode material as claimed in any one of claims 1 to 7, comprising:
adding conductive carbon and amorphous carbon into nano-silicon oxide, mixing, performing spray drying for secondary granulation, and performing high-temperature sintering carbonization to obtain a first mixture;
uniformly dispersing conductive carbon in a polymer solution to obtain a second mixture;
and dispersing the first mixture into the second mixture, stirring, adding an oxidant for in-situ polymerization, filtering the obtained material, cleaning and drying to obtain the silicon monoxide negative electrode material.
9. The preparation method according to claim 8, wherein the temperature of the high-temperature sintering carbonization is 600-800 ℃ and the time is 3 h;
preferably, the molar ratio of polymer to oxidant is 1: 1-1: 4.
10. a lithium ion battery comprising a member formed of the negative electrode material of silicon oxide according to any one of claims 1 to 7.
CN202010489504.XA 2020-06-02 2020-06-02 Silicon monoxide negative electrode material and preparation method and application thereof Pending CN111653746A (en)

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CN112038571A (en) * 2020-09-28 2020-12-04 合肥国轩高科动力能源有限公司 Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery
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Application publication date: 20200911