CN113745490B - Nano silicon-based composite fiber negative electrode material of lithium ion battery - Google Patents
Nano silicon-based composite fiber negative electrode material of lithium ion battery Download PDFInfo
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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- H—ELECTRICITY
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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 the technical field of lithium ion batteries, in particular to a nano silicon-based composite fiber cathode material of a lithium ion battery, which is characterized in that: comprises a nano-fiber matrix, nano-silicon-based active substance particles and a conductive polymer, wherein the nano-silicon-based active substance particles and the conductive polymer are uniformly dispersed in the nano-fiber matrix; the mass fraction of the nano fiber matrix is 5-97%, the mass fraction of the nano silicon-based active substance particles is 2-70%, and the mass fraction of the conductive polymer is 1-25%; the nanofiber matrix is obtained by electrostatic spinning of spinning solution formed by dissolving a polymer in an organic solvent; the nano silicon-based active particles are at least one of silicon-containing compounds or composites. Compared with the prior art, the method has the advantages of simple operation and environment-friendly process; and the prepared cathode material not only has higher electron conduction capability, but also can effectively relieve the volume expansion and the structural pulverization of the nano silicon-based active material particles and improve the cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nano silicon-based composite fiber cathode material of a lithium ion battery.
Background
The lithium ion battery has the advantages of good electrochemical performance, environmental protection, no pollution, low price and the like, and is widely used. The negative electrode material of the lithium ion battery is generally a graphite carbon material, which is close to the theoretical specific capacity (372 mAh/g) at present, but with the rapid development of the fields of portable electronic products and electric automobiles, the graphite carbon material is difficult to meet the ever-increasing demand of high energy density. In recent years, silicon-based materials such as Si, siOx/C, etc. have attracted more attention from researchers because the silicon-based materials have a theoretical specific capacity several times higher than that of graphite materials, and become a research focus and a development trend of lithium ion battery negative electrode materials in the future.
Although the silicon-based material has higher theoretical specific capacity, the volume change of the silicon-based material is huge under the condition of high-degree lithium extraction, so that the silicon-based material has the disadvantages of particle pulverization, reduced conductivity and poor cycle stability. At present, the solutions include carbon coating modification, porosification and alloying of silicon-based material particles. Although these methods have achieved certain results, the preparation methods are complex, not only is the preparation period long, but also high energy consumption processes such as high-temperature sintering are required. Therefore, a method which is simple to operate and environment-friendly in process is urgently needed in the field of silicon-based negative electrode materials of lithium ion batteries.
Electrospinning is an effective method for preparing nanofiber materials inexpensively and efficiently. The polymer precursor can form a uniform nanofiber structure after being processed by the method. Nano-scale fiber materials can be prepared. Through patent retrieval, the Chinese patent with the publication number of CN103305965B discloses a silicon-carbon composite material with nano-micropores and a preparation method and application thereof, wherein the silicon-carbon composite material with the nano-micropores structure is prepared by adopting a method of electrostatic spinning combined with oxidation and carbonization, so that a buffer space is reserved for the expansion of nano-silicon particles on the premise of ensuring the integral electron transmission capability of the material; the Chinese invention patent with application publication number CN104037390A discloses a preparation method of a titanium dioxide lithium battery anode material loaded by a silicon/carbon nanowire, wherein the titanium dioxide composite silicon/carbon nanowire anode material is obtained by adopting electrostatic spinning, oxidation and carbonization methods, and has high specific capacity and cycle performance; the Chinese invention patent with application publication number CN105118974A discloses a silicon-based negative electrode material and a preparation method thereof, and the carbon-coated silicon/carbon nano-fiber is prepared by adopting electrostatic spinning and multiple carbonization methods, so that the volume expansion and the structural fragmentation of silicon particles are relieved.
The three patents all carry out oxidation and carbonization processes after the nano composite fiber is obtained through the electrostatic spinning process, and aim to sinter the fiber matrix into carbon so as to improve the integral electronic conductivity of the material. However, the oxidation and carbonization processes are both high-temperature and high-energy-consumption processes, and the process is complicated and difficult to control due to the fact that the fiber material is subjected to heat treatment for many times under different temperatures and different atmospheres.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and the final lithium ion battery cathode material can be obtained only by carrying out vacuum drying on the composite nanofiber subjected to electrostatic spinning at a low temperature to remove a solvent; on one hand, the nano silicon-based active substance particles in the composite material are coated with the conductive polymer, so that the electronic conduction capability can be improved, and on the other hand, the nano fiber matrix can be used as secondary coating, so that the volume expansion and the structure pulverization of the nano silicon-based active substance particles can be effectively relieved, and the cycle performance is improved.
In order to realize the purpose, the nano silicon-based composite fiber cathode material of the lithium ion battery is designed, and is characterized in that:
comprises a nano-fiber matrix, nano-silicon-based active substance particles and a conductive polymer, wherein the nano-silicon-based active substance particles and the conductive polymer are uniformly dispersed in the nano-fiber matrix; the mass fraction of the nano fiber matrix is 5-97%, the mass fraction of the nano silicon-based active substance particles is 2-70%, and the mass fraction of the conductive polymer is 1-25%;
the nanofiber matrix is obtained by electrostatic spinning of spinning solution formed by dissolving a polymer in an organic solvent; the polymer is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyacrylonitrile, polyimide and polyvinylidene fluoride; the concentration of the polymer in the spinning solution is 5-20 wt%;
the nano silicon-based active particles are at least one of silicon-containing compounds or compounds;
the conductive polymer is one or more of polyaniline, polyparaphenylene, polypyrrole or polythiophene or derivatives of the polyaniline, the polyparaphenylene, the polypyrrole and the polythiophene; the conductive polymer state is a solid phase nanoparticle or a liquid phase solution.
The silicon-containing compound or the compound is at least one of Si, siOx, si-M alloy, si/C, siOx/C, si-M/C, wherein M is metal or metal oxide, and x is more than or equal to 0 and less than or equal to 2,C is organic carbon, inorganic carbon, graphite, graphene, carbon nano tubes or carbon fibers.
The diameter of the nano silicon-based active substance particles is 10-500nm.
The diameter of the nanofiber matrix is 100-1000nm.
The number average molecular weight of the conductive polymer is more than or equal to 1000 and less than or equal to 30 ten thousand.
The organic solvent is at least one of ethanol, dimethylformamide, dimethylacetamide or dimethyl sulfoxide.
The metal or metal oxide M is Li or Li 2 O、Co、CoO、Fe、Fe 2 O 3 、Mg、MgO、Sn、SnO、Ti、TiO 2 Ag, agO or Cr.
A preparation method of a nano silicon-based composite fiber cathode material of a lithium ion battery is characterized by comprising the following steps of: the preparation method comprises the following preparation steps:
(1) And mixing raw materials: uniformly mixing the nano silicon-based active substance particles with a conductive polymer to form a mixture H1;
(2) Preparing a spinning solution: stirring and dissolving a polymer in an organic solvent, and defoaming to prepare uniform spinning solution H2;
(3) Preparing a mixed spinning solution: stirring and dispersing the mixture H1 in the spinning solution H2 to obtain a uniform mixed spinning solution H3;
(4) And electrostatic spinning: and (3) filling the mixed spinning solution H3 into an injector, performing electrostatic spinning in a high-voltage electrostatic field, curing and molding the spinning solution trickle in the air, and then performing low-temperature vacuum drying to obtain the nano silicon-based composite fiber cathode material of the lithium ion battery.
The electric field voltage of the electrostatic spinning is 12-30kV; the flow rate of the spinning solution is 0.5-1.5mL/h; the spinning distance is 8-30cm; the temperature of the spinning environment is 25-30 ℃; the air humidity is 25-45%.
The nano silicon-based active substance particles and the conductive polymer in the raw material mixing are mixed in any one of a solid-phase mixing mode or a solid-liquid mixing mode, ball milling or mechanical stirring mixing is adopted when the solid phase is mixed, and centrifugation and ultrasonic mixing are adopted when the solid phase is mixed with the liquid phase.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
compared with the prior art, the final lithium ion battery cathode material can be obtained only by carrying out vacuum drying on the composite nanofiber subjected to electrostatic spinning at a low temperature to remove the solvent, and oxidation and carbonization processes with high temperature and high energy consumption are not needed, so that the operation is simple and the process is environment-friendly; the prepared nano silicon-based composite nanofiber negative electrode material for the lithium ion battery has high electron conduction capability, can effectively relieve volume expansion and structural pulverization of nano silicon-based active particles, and improves cycle performance.
Drawings
Fig. 1 is a schematic structural diagram of a nano silicon-based composite fiber negative electrode material of a lithium ion battery in embodiment 1 of the invention.
Fig. 2 is a first charge-discharge curve of the lithium ion battery nano silicon-based composite fiber negative electrode material prepared in example 2 of the present invention.
Fig. 3 is a schematic diagram of 50-cycle capacity retention rate of the nano silicon-based composite fiber negative electrode material of the lithium ion battery prepared in example 2 of the present invention.
Referring to fig. 1, wherein 100 is a nano silicon-based active particle; 200 is a conductive polymer; 300 is a nanofiber matrix.
Detailed Description
The present invention will be further described with reference to the following examples. It should be noted that the specific substances mentioned in the following examples are only given as examples, and are not limited thereto, that is, other substances with equivalent functions not listed in the examples of the present invention may be substituted under the same conditions.
Example 1
As shown in fig. 1, the lithium ion battery nano silicon-based composite fiber negative electrode material in the invention comprises a nano fiber matrix, nano silicon-based active material particles and a conductive polymer, wherein the conductive polymer and the nano silicon-based active material particles are mutually connected by hydrogen bond interaction and physical contact, and the nano silicon-based active material particles are bridged together by the conductive polymer.
Wherein, the mass fraction of the nano-fiber matrix is 5-97%, the mass fraction of the nano-silicon-based active substance particles is 2-70%, the mass fraction of the conductive polymer is 1-25%, the diameter of the nano-fiber matrix is 100-1000nm, and the average diameter of the nano-silicon-based active substance particles is preferably 10-500nm.
The nanofiber matrix is obtained by electrostatic spinning of spinning solution formed by dissolving a polymer in an organic solvent; the polymer is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyacrylonitrile, polyimide and polyvinylidene fluoride; and the concentration of the polymer in the spinning solution is 5-20 wt%; the organic solvent is at least one of ethanol, dimethylformamide, dimethylacetamide or dimethyl sulfoxide;
the nano silicon-based active particles are at least one of silicon-containing compounds or compounds; the silicon-containing compound or compound is at least one of Si, siOx, si-M alloy, si/C, siOx/C, si-M/C, wherein M is metal or metal oxide, and x is more than or equal to 0 and less than or equal to 2,C is organic carbon, inorganic carbon, graphite, graphene, carbon nano tubes or carbon fibers; the metal or metal oxide M is Li or Li 2 O、Co、CoO、Fe、Fe 2 O 3 、Mg、MgO、Sn、SnO、Ti、TiO 2 Ag, agO or Cr.
The conductive polymer is one or more of polyaniline, polyparaphenylene, polypyrrole or polythiophene or derivatives of the polyaniline, the polyparaphenylene, the polypyrrole and the polythiophene; the conductive polymer state is a solid phase nanoparticle or a liquid phase solution.
Further, the diameter of the nano silicon-based active substance particles is 10-500nm.
Further, the diameter of the nanofiber matrix is 100-1000nm.
Furthermore, the number average molecular weight of the conductive polymer is more than or equal to 1000 and less than or equal to 30 ten thousand.
Example 2
Putting 30g of nano Si with the particle size of 30nm and 2g of polyaniline powder into a ball mill for solid-phase mixing uniformly to obtain a mixture H1;
weighing 20g of polyacrylonitrile powder with the molecular weight Mw =15 ten thousand, adding the polyacrylonitrile powder into 200g of DMF, and stirring and dissolving for 8 hours at normal temperature to obtain a solution H2 with the mass fraction of 9%;
adding H1 into H2, stirring and dispersing for 5H to obtain a mixed spinning solution H3 with Si uniformly dispersed in a DMF (dimethyl formamide) solution of PAN;
adding H3 into an injector, extruding out the spinning solution at the flow rate of 0.9mL/H, performing electrostatic spinning under a high-voltage electric field of 15kV, wherein the receiving distance is 15cm, the ambient temperature is 25 ℃, the air humidity is 40%, the spinning trickle is cured and formed by air and collected on the surface of an aluminum foil, and then performing low-temperature vacuum drying at the temperature of 60 ℃ and the vacuum degree of 50mbar for 12H to remove the solvent, thereby obtaining the nano silicon-based composite fiber cathode material of the lithium ion battery.
Tests show that the mass specific capacity of the material reaches 2028mAh/g, the first effect is 82%, the capacity retention rate is above 76% after 50-week circulation, and the expansion rate of a pole piece is as low as below 50%, see fig. 3.
Example 3
20g of nano Si with the particle size of 40nm and 2g of polypyrrole powder are put into a mechanical stirrer to be uniformly mixed in a solid phase manner, so that a mixture H1 is obtained;
weighing 20g of polyacrylonitrile powder with the molecular weight Mw =15 ten thousand, adding the polyacrylonitrile powder into 200g of DMF, and stirring and dissolving for 8 hours at normal temperature to obtain a solution H2 with the mass fraction of 9%;
adding H1 into H2, stirring and dispersing for 6 hours to obtain a mixed spinning solution H3 in which Si is uniformly dispersed in a DMF (dimethyl formamide) solution of PAN (Polyacrylonitrile);
adding H3 into an injector, extruding out the spinning solution at the flow rate of 0.9mL/H, performing electrostatic spinning under a high-voltage electric field of 15kV, wherein the receiving distance is 15cm, the ambient temperature is 25 ℃, the air humidity is 40%, the spinning trickle is cured and formed by air and collected on the surface of an aluminum foil, and then performing low-temperature vacuum drying at the temperature of 60 ℃ and the vacuum degree of 50mbar for 12H to remove the solvent, thereby obtaining the nano silicon-based composite fiber cathode material of the lithium ion battery.
Tests show that the lithium ion battery prepared from the material has a specific mass capacity of 1831mAh/g, a first effect of 84%, a capacity retention rate of over 74% after 50-week circulation, and a pole piece expansion rate of below 50%.
Example 4
25g of nano Si with the particle size of 80nm and 100g of PEDOT: carrying out liquid phase mixing on the PSS solution by adopting ultrasound to obtain a uniform mixed solution H1; wherein, PEDOT: the PEDOT content in the PSS solution accounts for 1wt% of the PSS;
weighing 20g of polyacrylonitrile powder with the molecular weight Mw =18 ten thousand, adding the polyacrylonitrile powder into 200g of DMF, and stirring and dissolving for 8 hours at normal temperature to obtain a solution H2 with the mass fraction of 9%;
adding H1 into H2, stirring and dispersing for 8H to obtain a mixed spinning solution H3 with Si uniformly dispersed in a DMF (dimethyl formamide) solution of PAN;
adding the mixed spinning solution into an injector, extruding the spinning solution at the flow rate of 1.0mL/h, performing electrostatic spinning under a high-voltage electric field of 15kV, wherein the receiving distance is 16cm, the ambient temperature is 30 ℃, the air humidity is 35%, the spinning trickle is cured and formed by air and collected on the surface of an aluminum foil, and then performing low-temperature vacuum drying at the temperature of 60 ℃ and the vacuum degree of 50mbar for 12h to remove the solvent, thereby obtaining the nano silicon-based composite fiber cathode material of the lithium ion battery.
Tests show that the lithium ion battery prepared from the material has a specific mass capacity of 1753mAh/g, a first effect of 87%, a capacity retention rate of more than 77% after 50-week circulation, and a pole piece expansion rate of less than 50%.
The foregoing is illustrative of the present invention and is not to be construed as limiting thereof. It will be apparent to those skilled in the art that various equivalent substitutions and obvious modifications can be made without departing from the spirit of the invention, and all such equivalents and modifications are deemed to fall within the scope of the invention.
Claims (10)
1. A nanometer silicon-based composite fiber negative electrode material of a lithium ion battery is characterized in that:
the nano silicon-based composite material comprises a nano fiber matrix, nano silicon-based active substance particles and a conductive polymer, wherein the nano silicon-based active substance particles and the conductive polymer are uniformly dispersed in the nano fiber matrix; the mass fraction of the nano fiber matrix is 5-97%, the mass fraction of the nano silicon-based active substance particles is 2-70%, and the mass fraction of the conductive polymer is 1-25%; the conductive polymer coats the nano silicon-based active particles;
the nanofiber matrix is obtained by electrostatic spinning of spinning solution formed by dissolving a polymer in an organic solvent; the polymer is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyacrylonitrile, polyimide and polyvinylidene fluoride; and the concentration of the polymer in the spinning solution is 5-20 wt%;
the nano silicon-based active particles are at least one of silicon-containing compounds or compounds;
the conductive polymer is one or more of polyaniline, polyparaphenylene, polypyrrole or polythiophene or derivatives of the polyaniline, the polyparaphenylene, the polypyrrole and the polythiophene; the conductive polymer state is a solid phase nanoparticle or a liquid phase solution.
2. The lithium ion battery nano silicon-based composite fiber negative electrode material of claim 1, characterized in that:
the silicon-containing compound or the compound is at least one of Si, siOx, si-M alloy, si/C, siOx/C, si-M/C, wherein M is metal or metal oxide, and x is more than or equal to 0 and less than or equal to 2,C is organic carbon, inorganic carbon, graphite, graphene, carbon nano tubes or carbon fibers.
3. The nano silicon-based composite fiber negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the diameter of the nano silicon-based active substance particles is 10-500nm.
4. The nano silicon-based composite fiber negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the diameter of the nanofiber matrix is 100-1000nm.
5. The nano silicon-based composite fiber negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the number average molecular weight of the conductive polymer is more than or equal to 1000 and less than or equal to 30 ten thousand.
6. The nano silicon-based composite fiber negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the organic solvent is at least one of ethanol, dimethylformamide, dimethylacetamide or dimethyl sulfoxide.
7. The nano silicon-based composite fiber negative electrode material of the lithium ion battery as claimed in claim 2, wherein: the metal or metal oxide M is Li or Li 2 O、Co、CoO、Fe、Fe 2 O 3 、Mg、MgO、Sn、SnO、Ti、TiO 2 Ag, agO or Cr.
8. The nano silicon-based composite fiber negative electrode material of the lithium ion battery as claimed in claim 1, wherein: the preparation method of the anode material comprises the following preparation steps:
(1) And mixing raw materials: uniformly mixing the nano silicon-based active substance particles with a conductive polymer to form a mixture H1;
(2) Preparing a spinning solution: stirring and dissolving a polymer in an organic solvent, and defoaming to prepare uniform spinning solution H2;
(3) Preparing a mixed spinning solution: stirring and dispersing the mixture H1 in the spinning solution H2 to obtain a uniform mixed spinning solution H3;
(4) And electrostatic spinning: and (3) filling the mixed spinning solution H3 into an injector, performing electrostatic spinning in a high-voltage electrostatic field, curing and molding the spinning solution trickle in the air, and then performing vacuum drying at 60 ℃ to obtain the lithium ion battery nano silicon-based composite fiber cathode material.
9. The nano silicon-based composite fiber negative electrode material of a lithium ion battery as claimed in claim 8, wherein: the electric field voltage of the electrostatic spinning is 12-30kV; the flow rate of the spinning solution is 0.5-1.5mL/h; the spinning distance is 8-30cm; the temperature of the spinning environment is 25-30 ℃; the air humidity is 25-45%.
10. The nano silicon-based composite fiber negative electrode material of a lithium ion battery as claimed in claim 8, wherein: the nanometer silicon-based active substance particles and the conducting polymer in the raw material mixing are mixed in any one of a solid phase mixing mode and a solid-liquid phase mixing mode, when the solid phase is mixed, ball milling or mechanical stirring mixing is adopted, and when the solid phase is mixed, centrifugation and ultrasonic mixing are adopted.
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| CN111916686B (en) * | 2019-05-08 | 2022-08-12 | 中国石油化工股份有限公司 | Phosphorus-containing lithium ion battery cathode material and preparation process thereof |
| CN110739454B (en) * | 2019-09-26 | 2021-04-02 | 山东玉皇新能源科技有限公司 | Negative electrode material and preparation method thereof |
| CN112635762B (en) * | 2019-10-09 | 2023-08-04 | 中国石油化工股份有限公司 | Lithium ion battery negative electrode material, preparation method and application thereof, and lithium ion battery |
| CN111816852B (en) * | 2020-06-29 | 2022-04-29 | 瑞声科技（南京）有限公司 | Preparation method of silicon-based composite negative electrode material |
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| CN114267493B (en) * | 2022-01-29 | 2023-05-19 | 深圳市明盛威先导科技有限公司 | Nitrogen-doped graphene-based aqueous conductive paste and preparation method and application thereof |
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