CN106941153B - Cotton-like elemental silicon nanowire cluster/carbon composite negative electrode material and preparation method and application thereof - Google Patents
Cotton-like elemental silicon nanowire cluster/carbon composite negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of battery materials, in particular to a cotton-shaped single substance silicon nano wire coil/carbon composite cathode material and a preparation method and application thereof, wherein the cotton-shaped single substance silicon nano wire coil/carbon composite cathode material is a cotton-shaped structure formed by integrating single substance silicon nano wires or/and single substance silicon nano particles, the outer surface and the gaps of the single substance silicon nano wire coil are coated with a conductive carbon material or a mixed conductive material to form a lithium ion battery cathode material, and at least one conductive material is contained in the mixed conductive material; the preparation method comprises the steps of preparing a polymer solution, uniformly mixing the polymer solution with the cotton-shaped elemental silicon nanowire clusters, filtering, drying, carbonizing, crushing and sieving to obtain the cotton-shaped elemental silicon nanowire cluster/carbon composite negative electrode material for the battery negative electrode of the lithium battery, and has the advantages that: the production is pollution-free, the explosion-proof internal stress release space is provided, the direct contact between silicon particles and electrolyte can be avoided, the capacity attenuation speed is slowed down, and the first charge-discharge efficiency, the first charge-discharge capacity and the cycle performance are improved.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a cotton-shaped single substance silicon nanowire cluster/carbon composite anode material with high capacity and good long-cycle stability, and a preparation method and application thereof.
Background
With the rapid expansion of population and the rapid development of economy, the electrochemical energy storage taking a lithium ion battery as a main expression form is greatly concerned and favored by the characteristics of environmental friendliness, long cycle life, small self-discharge, high energy density, high voltage and the like, and is widely applied to various portable electronic products, however, due to the influence of the energy storage mechanism and low capacity of the existing graphite cathode material, the existing commercial lithium ion battery is difficult to meet the use requirements of new energy automobile power batteries and the like on high energy density, and the simple substance silicon is the cathode material (4200mAh/g) with the highest known theoretical capacity, which is higher than the commercial graphite cathode (372 mAh/g). Meanwhile, the material has abundant earth crust storage and proper working voltage, and is considered to be the most potential preferred material for the high-capacity negative electrode material.
However, silicon as a semiconductor material has poor conductivity to lithium ions and electrons, and the volume expansion of particles in the charging and discharging process is as high as 0-300% due to the alloying reaction of silicon and lithium, which easily causes the damage of an electrode structure and the severe attenuation of battery capacity, and the problems seriously limit the large-scale use of silicon as a negative electrode material and reduce the silicon particles to the nano size below 100 nm. The silicon particles greatly reduce the volume expansion rate of silicon after the particles are subjected to nanocrystallization, the expansion rate of 60nm nanometer silicon is about 0-55% so as to reduce the internal stress of the electrode, and the silicon particles are compounded with a conductive carbon material, so that the electrochemical performance of the electrode can be effectively improved, and the silicon particles are also the mainstream direction adopted in the research of high-capacity and high-performance silicon cathode materials at present.
In the prior art, the nano silicon is prepared by mainly using chemical reactions such as silicon monoxide, silicon dioxide, tetrachlorohydrosilicon, silicon monoxide and the like to reduce to prepare nano silicon below nano level (100nm), the scale of the equipment is huge, the environmental pollution is great, the laboratory is feasible in small-scale trial production, but the industrial mass production brings a plurality of technical bottleneck problems, and the industrial mass production cannot be implemented at all.
The current situation of global new energy automobiles is that vehicle and enterprise subsidies are carried out by governments of various countries, new energy automobiles are developed by adopting encouraging policies, but the new energy automobiles are infeasible to depend on government financial subsidies for a long time. The method aims to solve the problem of rapid development of new energy automobiles, and firstly, the energy density of automobile power batteries must be improved, the endurance mileage is improved, so that the problem that ordinary people can not travel long distance after buying new energy automobiles due to fear of one-time charging can be solved, the real market rapid development of the new energy automobiles can be solved, and China can really become a strong country for manufacturing the new energy automobiles.
The Chinese patent publication numbers in the prior art are as follows: CN106058207A (university of science and technology in china), CN106252622A (fibrate), CN104466185A (shenzhen advanced technology research institute of china academy of science), CN104362311A (shenzhen research institute of qinghua university), CN102509781A (shanghai university of transportation), CN103545493A (zhongnan university), CN10331522A (institute of process engineering of china academy of science), and CN102790204A (institute of nigh materials of china academy of science and technology).
Disclosure of Invention
The invention aims to provide a cotton flocculent elemental silicon nanowire cluster/carbon composite anode material, a preparation method and application thereof.
The purpose of the invention is realized as follows:
the cotton-shaped single substance silicon nanowire cluster/carbon composite cathode material is characterized in that the single substance silicon nanowire cluster is of a cotton-shaped structure formed by gathering single substance silicon nanowires, conductive carbon materials or mixed conductive materials are coated on the outer surface of the single substance silicon nanowire cluster and in gaps of the single substance silicon nanowire cluster to form a lithium ion battery cathode material, and at least one conductive material is contained in the mixed conductive materials.
The simple substance silicon nanowire cluster is a cotton-shaped structure formed by gathering simple substance silicon nanoparticles, conductive carbon materials or mixed conductive materials are coated on the outer surface of the simple substance silicon nanowire cluster and in gaps of the simple substance silicon nanowire cluster to form a lithium ion battery cathode material, and at least one conductive material is contained in the mixed conductive materials.
The simple substance silicon nanowire cluster is a cotton-shaped structure formed by integrating simple substance silicon nanoparticles and simple substance silicon nanowires, conductive carbon materials or mixed conductive materials are coated on the outer surface of the simple substance silicon nanowire cluster and in gaps of the simple substance silicon nanowire cluster to form a lithium ion battery cathode material, and at least one conductive material is contained in the mixed conductive materials.
In the structure of the elemental silicon nanowire cluster, the mass of the elemental silicon nanowire with the diameter of 15nm-300nm accounts for more than 50% of the total mass of the elemental silicon nanowire cluster; in the structure of the elemental silicon nanowire clusters, the mass of the elemental silicon nanowire clusters with the diameter of 0.5-100 μm accounts for more than 50% of the total mass of the elemental silicon nanowire clusters.
The conductive carbon material is a carbon material into which one or more of the following high-molecular polymer materials are converted: phenolic resin, asphalt, glucose, sucrose, starch, polyacrylonitrile, polymethyl methacrylate and polyvinyl chloride; or a carbon material into which the conductive carbon material is converted from one or a combination of the following gases: methane gas, ethane gas, propane gas, propylene gas, acetylene gas and propyne gas.
The preparation method of the cotton flocculent simple substance silicon nanowire cluster comprises the following steps:
(1) putting high-purity silicon with the purity of 98-99.9999% into a reactor in a steam reaction furnace, heating the high-purity silicon into gaseous high-purity silicon by using a plasma spray gun in the reactor, allowing the gaseous high-purity silicon to enter a growth controller through a pipeline to grow into cotton flocculent elemental silicon nano-wire clusters with controlled sizes, allowing the cotton flocculent elemental silicon nano-wire clusters and gas in the reactor to enter a collector through a pipeline together, performing gas-solid separation to obtain solid cotton flocculent elemental silicon nano-wire clusters, communicating a pipeline communicated with a gas outlet of the collector with a vacuum pump, an exhaust fan and a heat exchanger, communicating cooling gas passing through the heat exchanger with an inner cavity of the reactor through the reaction furnace, and communicating a discharge port of a storage barrel and a feed pipe of the growth controller with the inner cavity of the reactor through the reactor; the feeding pipeline at the front part of the growth controller is a front feeding pipe, the discharging pipeline at the rear part is a rear discharging pipe, and the ratio of the length of the front feeding pipe to the inner diameter of the growth controller is (0.1-10): 1, the length of the front feeding pipe refers to the length of a pipeline leading the inner wall of the reactor to the inner wall of the inlet of the growth controller, and the ratio of the inner diameter of the front feeding pipe to the inner diameter of the growth controller is (0.05-0.8): 1; controlling the conglomeration size of the cotton flocculent elemental silicon nanowire clusters by controlling the flow, the flow direction and the cooling speed of the materials entering and exiting the growth controller, thereby obtaining the required cotton flocculent elemental silicon nanowire clusters;
(2) opening a discharge valve port of the collector, and taking out the cotton flocculent elemental silicon nanowire clusters; the purity of the cotton-shaped simple substance silicon nanowire cluster is 98-99.9999%.
The preparation method of the cotton-shaped elemental silicon nanowire cluster/carbon composite anode material comprises the following steps:
(1) preparing a polymer solution: weighing simple substance silicon nanowire clusters and medium and high molecular polymers, wherein the simple substance silicon nanowire clusters account for 10% -90%, the medium and high molecular polymers account for 10% -90% by weight, and dissolving the weighed medium and high molecular polymers in a solvent to obtain a polymer solution with the weight of 1-30%;
(2) loading the elemental silicon nanowire clusters weighed in the step (1) into the medium-high molecular polymer solution prepared in the step (1) for mechanical stirring, uniform dispersion and mixing, or mechanical emulsification, dispersion and mixing, or ultrasonic uniform dispersion and mixing to obtain a mixed solution;
(3) pumping the mixed solution prepared in the step (2) to a pressure container with the temperature of 150-;
(4) and (4) filtering or baking the uniform mixed solution prepared in the step (3) by using a solvent or drying the uniform mixed solution after filtering to obtain a mixture material.
(5) Carbonizing: and (3) putting the mixed solution prepared in the step (4) into a material boat, putting the material boat into a heating reaction furnace, baking and heating the material boat to the temperature of 900-1600 ℃ under the protection of inert gas, preserving the heat for 2-24 hours, carrying out carbonization reaction on the mixture, naturally cooling the mixture to the temperature below 200 ℃ or to the natural atmospheric temperature, taking out the material after the carbonization reaction, crushing and sieving the material to obtain the cotton flocculent elemental silicon nano coil/carbon composite cathode material.
The reaction furnace is one of a vacuum tube furnace, a rotary furnace, a roller kiln, a push plate kiln and heating reaction equipment; the inert gas is one of nitrogen, neon, argon and helium or the combination thereof.
The cotton-shaped elemental silicon nanowire cluster/carbon composite cathode material is used for a battery cathode of a lithium battery.
The lithium battery comprises a battery anode, a battery cathode, electrolyte and a diaphragm, wherein the battery cathode is made of the lithium battery cathode material.
Compared with the prior art, the invention has the outstanding and beneficial technical effects that:
1. the elemental silicon (Si) flocculent nanowire cluster prepared by the invention grows and forms under the Physical Vapor Deposition (PVD) vacuum closed environment condition without adopting any chemical substance, and does not cause any pollution to the atmospheric environment and soil.
2. The cotton-shaped single substance silicon nanowire cluster prepared by the invention solves the expansion coefficient problem of the silicon material in the lithium ion battery cathode material in the charging and discharging de-intercalation process and the space problem of no internal stress release in the expansion process, and avoids the damage (such as explosion and the like) of the electric plate structure caused by the crushing of the silicon material.
3. The flocculent simple substance silicon nanowire cluster prepared by the invention has the advantages that the single particle size is 0.5-100 mu m (figure 2), the dispersion treatment is very easy, and the carbon source material is easy to coat the surface of the flocculent simple substance silicon nanowire cluster. If the single particle size of the nano silicon is 20-100nm, although the expansion rate problem is greatly reduced, the single particle size is too small to be uniformly dispersed, so that the carbon source material is difficult to uniformly coat the surface of the nano silicon.
4. The novel high-specific-capacity lithium ion battery cathode material developed by the invention is used for carrying out asphalt softening and coating on nano silicon, so that direct contact between silicon particles and electrolyte can be avoided, the capacity attenuation speed is reduced, meanwhile, the diffusion path of lithium ions is shortened, the electronic conduction of the electrode material is ensured not to be lost, and the first charge-discharge efficiency, the charge-discharge capacity and the cycle performance are improved.
Drawings
Fig. 1 is an electron microscope observation photograph of elemental silicon nanowires of the present invention.
FIG. 2 is an electron microscope observation photograph of the elemental silicon nanowire clusters of the cotton-like structure integrated by the elemental silicon nanowires of the present invention.
Fig. 3 is a graph of a relationship curve (solid line) between the first charge specific capacity of the lithium ion battery manufactured in example 1 of the present invention, the first discharge specific capacity of the lithium ion battery reaches 2392mAh/g, the first discharge specific capacity of the lithium ion battery is 2033mAh/g, and the discharge specific capacity and the discharge frequency of the lithium ion battery after 100 cycles of charge and discharge, wherein a dotted line in the graph is an indication line.
Fig. 4 is a graph of a relationship curve (solid line) between the first charge specific capacity of the lithium ion battery manufactured in example 4 of the present invention, the first discharge specific capacity of the lithium ion battery, and the discharge specific capacity and the discharge frequency of the lithium ion battery, wherein the dashed line is an indication line.
Fig. 5 is one of electron microscope observation photographs of elemental silicon nanowire clusters of a cotton-like structure aggregated with elemental silicon nanoparticles.
Fig. 6 is a second electron microscope observation photograph of the elementary silicon nanowire cluster of the cotton-like structure aggregated by the elementary silicon nanoparticles.
Fig. 7 is an electron microscope observation photograph of a plurality of elemental silicon nanowire clusters of a cotton-like structure aggregated with elemental silicon nanoparticles to show that the elemental silicon nanowire clusters have different sizes.
Detailed Description
Referring to fig. 1-7:
the cotton-shaped single substance silicon nanowire cluster/carbon composite cathode material is characterized in that the single substance silicon nanowire cluster is of a cotton-shaped structure formed by gathering single substance silicon nanowires, conductive carbon materials or mixed conductive materials are coated on the outer surface of the single substance silicon nanowire cluster and in gaps of the single substance silicon nanowire cluster to form a lithium ion battery cathode material, and at least one conductive material is contained in the mixed conductive materials.
The simple substance silicon nanowire cluster is a cotton-shaped structure formed by gathering simple substance silicon nanoparticles, conductive carbon materials or mixed conductive materials are coated on the outer surface of the simple substance silicon nanowire cluster and in gaps of the simple substance silicon nanowire cluster to form a lithium ion battery cathode material, and at least one conductive material is contained in the mixed conductive materials.
The simple substance silicon nanowire cluster is a cotton-shaped structure formed by integrating simple substance silicon nanoparticles and simple substance silicon nanowires, conductive carbon materials or mixed conductive materials are coated on the outer surface of the simple substance silicon nanowire cluster and in gaps of the simple substance silicon nanowire cluster to form a lithium ion battery cathode material, and at least one conductive material is contained in the mixed conductive materials.
In the structure of the elemental silicon nanowire cluster, the mass of the elemental silicon nanowire with the diameter of 15nm-300nm accounts for more than 50% of the total mass of the elemental silicon nanowire cluster; in the structure of the elemental silicon nanowire clusters, the mass of the elemental silicon nanowire clusters with the diameter of 0.5-100 μm accounts for more than 50% of the total mass of the elemental silicon nanowire clusters.
The conductive carbon material is a carbon material into which one or more of the following high-molecular polymer materials are converted: phenolic resin, asphalt, glucose, sucrose, starch, polyacrylonitrile, polymethyl methacrylate and polyvinyl chloride; or a carbon material into which the conductive carbon material is converted from one or a combination of the following gases: methane gas, ethane gas, propane gas, propylene gas, acetylene gas and propyne gas.
The preparation method of the cotton flocculent simple substance silicon nanowire cluster comprises the following steps:
(1) putting high-purity silicon with the purity of 98-99.9999% into a reactor in a steam reaction furnace, heating the high-purity silicon into gaseous high-purity silicon by using a plasma spray gun in the reactor, allowing the gaseous high-purity silicon to enter a growth controller through a pipeline to grow into cotton flocculent elemental silicon nano-wire clusters with controlled sizes, allowing the cotton flocculent elemental silicon nano-wire clusters and gas in the reactor to enter a collector through a pipeline together, performing gas-solid separation to obtain solid cotton flocculent elemental silicon nano-wire clusters, communicating a pipeline communicated with a gas outlet of the collector with a vacuum pump, an exhaust fan and a heat exchanger, communicating cooling gas passing through the heat exchanger with an inner cavity of the reactor through the reaction furnace, and communicating a discharge port of a storage barrel and a feed pipe of the growth controller with the inner cavity of the reactor through the reactor; the feeding pipeline at the front part of the growth controller is a front feeding pipe, the discharging pipeline at the rear part is a rear discharging pipe, and the ratio of the length of the front feeding pipe to the inner diameter of the growth controller is (0.1-10): 1, the length of the front feeding pipe refers to the length of a pipeline leading the inner wall of the reactor to the inner wall of the inlet of the growth controller, and the ratio of the inner diameter of the front feeding pipe to the inner diameter of the growth controller is (0.05-0.8): 1; controlling the conglomeration size of the cotton flocculent elemental silicon nanowire clusters by controlling the flow, the flow direction and the cooling speed of the materials entering and exiting the growth controller, thereby obtaining the required cotton flocculent elemental silicon nanowire clusters;
(2) opening a discharge valve port of the collector, and taking out the cotton flocculent elemental silicon nanowire clusters; the purity of the cotton-shaped simple substance silicon nanowire cluster is 98-99.9999%.
The reactor is a crucible container made of high-temperature resistant materials such as zirconia, graphite, quartz, alloy and the like.
The preparation method of the cotton-shaped elemental silicon nanowire cluster/carbon composite anode material comprises the following steps:
(1) preparing a polymer solution: weighing simple substance silicon nanowire clusters and medium and high molecular polymers, wherein the simple substance silicon nanowire clusters account for 10% -90%, the medium and high molecular polymers account for 10% -90% by weight, and dissolving the weighed medium and high molecular polymers in a solvent to obtain a polymer solution with the weight of 1-30%;
(2) loading the elemental silicon nanowire clusters weighed in the step (1) into the medium-high molecular polymer solution prepared in the step (1) for mechanical stirring, uniform dispersion and mixing, or mechanical emulsification, dispersion and mixing, or ultrasonic uniform dispersion and mixing to obtain a mixed solution;
(3) pumping the mixed solution prepared in the step (2) to a pressure container with the temperature of 150-;
(4) and (4) filtering or baking the uniform mixed solution prepared in the step (3) by using a solvent or drying the uniform mixed solution after filtering to obtain a mixture material.
(5) Carbonizing: and (3) putting the mixed solution prepared in the step (4) into a material boat, putting the material boat into a heating reaction furnace, baking and heating the material boat to the temperature of 900-1600 ℃ under the protection of inert gas, preserving the heat for 2-24 hours, carrying out carbonization reaction on the mixture, naturally cooling the mixture to the temperature below 200 ℃ or to the natural atmospheric temperature, taking out the material after the carbonization reaction, crushing and sieving the material to obtain the cotton flocculent elemental silicon nano coil/carbon composite cathode material.
The reaction furnace is one of a vacuum tube furnace, a rotary furnace, a roller kiln, a push plate kiln and heating reaction equipment; the inert gas is one of nitrogen, neon, argon and helium or the combination thereof.
The cotton-shaped elemental silicon nanowire cluster/carbon composite cathode material is used for a battery cathode of a lithium battery.
The lithium battery comprises a battery anode, a battery cathode, electrolyte and a diaphragm, wherein the battery cathode is made of the lithium battery cathode material.
For a better understanding of the present invention, the invention is further described in the following with reference to specific embodiments thereof, but for the sake of easy reading, some of which are simplified and the detailed process can be referred to above:
example 1:
weighing 2 g of high-temperature petroleum asphalt (provided by Lvtege (Shanghai) trade company Limited) and dissolving the petroleum asphalt in 150ML ethanol to obtain a polymer solution, adding 4 g of cotton-shaped flocculent elemental silicon nano-wire clusters, and carrying out mechanical emulsification, dispersion, stirring and mixing for 10-120 min to fully disperse and mix the cotton-shaped flocculent elemental silicon nano-wire clusters in the polymer solution, pumping the obtained fully-dispersed and uniformly-mixed solution into a high-temperature pressure container to further disperse and mix the solution uniformly, so that the asphalt mixture solution can be better coated on the cotton-shaped flocculent elemental silicon nano-wire clusters.
Filtering a solvent in a high-temperature pressure container to obtain a viscous mixture, namely a high-temperature petroleum asphalt coated flocculent elemental silicon nanowire cluster composite material, transferring the mixture into a material placing boat, placing the material into a vacuum tube type heating furnace under the protection of argon atmosphere, heating to 1150 ℃, preserving heat for 4 hours, carrying out carbonization reaction on asphalt in the process, cooling, taking out 5.9 of the composite material, crushing and sieving to obtain the flocculent elemental silicon nanowire cluster/carbon composite cathode material.
The content of the cotton flocculent elemental silicon nanowire cluster in the composite anode material is measured to be 68% by a thermogravimetric analyzer.
The obtained cotton-shaped elemental silicon nanowire coil/carbon composite negative electrode material is respectively mixed with a conductive agent acetylene black and a binding agent PVDF according to the mass percentage of 79:10:11, wherein 2.37g of the cotton-shaped elemental silicon nanowire coil/carbon composite negative electrode material, 0.3g of acetylene black and 0.33g of PVDFF are weighed, the mixture is mixed into slurry by using NMP (1-methyl-2-pyrrole cyclic ketone), the slurry is uniformly coated on copper foil, vacuum drying is carried out at 110 ℃ for 20 hours, a pole piece for an experimental battery is prepared, a lithium piece is taken as a corresponding electrode, 1mol/L of electrolyte, 1:1 of volume ratio of EC (ethyl carbonate) + dimethyl carbonate of LIPEC, a diaphragm is a Lelgard2400 membrane, and a CR2025 button cell is prepared in a glove box filled with argon atmosphere.
As shown in FIG. 3, the battery manufactured according to this example has a first charging specific capacity of 2392mAh/g, a first discharging specific capacity of 2033mAh/g, a second charging specific capacity of 1913mAh/g, and a second discharging specific capacity of 1735 mAh/g.
The method is mainly caused by that a Solid Electrolyte Interface (SEI) film is generated in the first discharging process and part of irreversible reaction, such as part of simple substance silicon nanowire hollow cotton particles which are not coated by carbon crack and fall off, and a small amount of oxygen in the composite material can be combined with lithium to generate lithium oxide. However, the specific capacity attenuation of the battery is not obvious along with the increase of the cycle times after the first charging and discharging, and the discharge capacity is still kept at 1659mAh/g after 100 cycles, which shows that the carbon shell of the cotton flocculent simple substance silicon nanowire ball/carbon composite material effectively inhibits the volume expansion effect of silicon and improves the cycle performance of the lithium ion battery.
Example 2:
(1) weighing 2 g of high-temperature petroleum asphalt (provided by Lvtege (Shanghai) trade company Limited) and dissolving the petroleum asphalt in 150ML ethanol to obtain a polymer solution, adding 2 g of cotton-shaped flocculent elemental silicon nano-wire clusters, and carrying out mechanical emulsification, dispersion, stirring and mixing for 10-120 min to fully disperse and mix the cotton-shaped flocculent elemental silicon nano-wire clusters in the polymer solution, pumping the obtained fully-dispersed and uniformly-mixed solution into a high-temperature pressure container to further disperse and mix the solution uniformly, so that the asphalt mixture solution can be better coated on the cotton-shaped flocculent elemental silicon nano-wire clusters.
(2) Filtering a solvent in a high-temperature pressure container to obtain a viscous mixture, namely the high-temperature petroleum asphalt coated flocculent elemental silicon nano-wire coil composite material, transferring the viscous mixture into a discharge porcelain boat, putting the discharge porcelain boat into a vacuum tube type heating furnace under the protection of argon atmosphere, heating to 1150 ℃, preserving heat for 4 hours, allowing the asphalt to perform carbonization reaction in the process, cooling, and taking out 3.9 g of the porous conductive carbon coated flocculent elemental silicon nano-wire coil composite material.
(3) The content of the flocculent elemental silicon nanowire clusters contained in the composite material is 52 percent through thermogravimetric analysis.
(4) The obtained flocculent elemental silicon nanowire roll/carbon composite negative electrode material is respectively mixed with a conductive agent acetylene black and a binding agent PVDF according to the mass percentage of 79:10:11, wherein 2.37g of the elemental silicon nanowire hollow cotton/carbon negative electrode material, 0.3g of the acetylene black and 0.33g of PVDFF are weighed, the mixture is mixed into slurry by using NMP (1-methyl-2-pyrrole cyclic ketone), the slurry is uniformly coated on copper foil, vacuum drying is carried out at 110 ℃ for 20 hours, a pole piece for an experimental battery is prepared, a lithium piece is taken as a corresponding electrode, 1mol/L of electrolyte, 1:1 volume ratio of EC (ethyl carbonate) + DMC (dimethyl carbonate) of LIPEC, and a diaphragm is a Lelgard2400 membrane, and the 202CR 5 button battery is prepared in a glove box filled with argon atmosphere.
(5) The battery manufactured according to the embodiment has the specific capacity of the first charge up to 1885mAh/g, the specific capacity of the first discharge up to 1658.8mAh/g, the specific capacity of the second charge up to 1715mAh/g and the ratio of the second discharge up to 1542mAh/g.
The method is mainly caused by that a Solid Electrolyte Interface (SEI) film is generated in the first discharging process and part of irreversible reaction, such as part of carbon uncoated simple substance silicon nanowire hollow cotton particles are cracked and fall off, and a small amount of oxygen in the composite material can be combined with lithium to generate lithium oxide. However, the specific capacity attenuation of the battery is not obvious along with the increase of the cycle times after the first charging and discharging, and the discharge capacity is still kept at 1563mAh/g after 100 cycles, which shows that the carbon shell of the cotton flocculent elemental silicon nanowire roll/carbon composite material effectively inhibits the volume expansion effect of silicon and improves the cycle performance of the lithium ion battery.
Example 3:
(1) weighing 2 g (supplied by the market) of glucose with the concentration of 85 percent and dissolving the glucose in 120ml of ethanol to form a glucose solution, adding 4 g of cotton-shaped single substance silicon nano-coil and uniformly stirring to ensure that the glucose solution is better coated on the cotton-shaped single substance silicon nano-coil;
(2) carbonizing, cooling, taking out 5.7 g of carbon-coated flocculent elemental silicon nanowire clusters, crushing and sieving to obtain flocculent elemental silicon nanowire cluster/carbon composite negative electrode materials;
(3) wherein: the content of cotton-shaped single substance silicon nanowire clusters is 70 percent;
(4) respectively mixing the obtained cotton-shaped single substance silicon nanowire coil/carbon composite negative electrode material with a conductive agent acetylene black and a binding agent PVDF (polyvinylidene fluoride) according to the mass percentage of 79:10:11, weighing 2.37g of the cotton-shaped single substance silicon nanowire coil/carbon composite negative electrode material, 0.3g of acetylene black and 0.33g of PVDFF, mixing the mixture into slurry by using NMP (1-methyl-2-pyrrole cyclic ketone), uniformly coating the slurry on a copper foil, performing vacuum drying at 110 ℃ for 20 hours to prepare a pole piece for an experimental battery, taking a lithium piece as a corresponding electrode, 1mol/L of electrolyte, 1:1 volume ratio of EC (ethyl carbonate) + dimethyl carbonate of LIEC (dimethyl carbonate), and taking a diaphragm as a Lelgard2400 membrane, and filling a glove box filled with argon atmosphere into a CR2025 button cell;
(5) the battery manufactured according to the embodiment has the first charging specific capacity of 2420mAh/g, the first discharging specific capacity of 1985mAh/g, the second charging specific capacity of 1936mAh/g and the second discharging ratio of 1645.6mAh/g, which are mainly caused by that a solid electrolyte film (SEI) film and part of irreversible reaction are generated in the first discharging process, for example, part of carbon uncoated simple substance silicon nanowire hollow cotton particles crack and fall off, and the composite material has high oxygen content and can be combined with lithium to generate lithium oxide. However, the specific capacity attenuation of the battery is not obvious along with the increase of the cycle times after the first charging and discharging, and the discharge capacity is still kept at 1563mAh/g after 100 cycles, which shows that the carbon shell of the cotton flocculent elemental silicon nanowire roll/carbon composite material effectively inhibits the volume expansion effect of silicon and improves the cycle performance of the lithium ion battery.
Example 4:
(1) weighing 2 g (supplied by the market) of glucose with the concentration of 85 percent and dissolving the glucose in 120ml of ethanol to form a glucose solution, adding 2 g of cotton-shaped single substance silicon nano-coil and uniformly stirring to ensure that the glucose solution is better coated on the cotton-shaped single substance silicon nano-coil;
(2) carbonizing, cooling, taking out 3.7 g of carbon-coated flocculent elemental silicon nanowire clusters, crushing and sieving to obtain flocculent elemental silicon nanowire cluster/carbon composite negative electrode materials;
(3) wherein: the content of cotton-shaped single substance silicon nanowire clusters is 54 percent;
(4) respectively mixing the obtained cotton-shaped single substance silicon nanowire coil/carbon composite negative electrode material with a conductive agent acetylene black and a binding agent PVDF (polyvinylidene fluoride) according to the mass percentage of 79:10:11, weighing 2.37g of the cotton-shaped single substance silicon nanowire coil/carbon composite negative electrode material, 0.3g of acetylene black and 0.33g of PVDFF, mixing the mixture into slurry by using NMP (1-methyl-2-pyrrole cyclic ketone), uniformly coating the slurry on a copper foil, performing vacuum drying at 110 ℃ for 20 hours to prepare a pole piece for an experimental battery, taking a lithium piece as a corresponding electrode, 1mol/L of electrolyte, 1:1 volume ratio of EC (ethyl carbonate) + dimethyl carbonate of LIEC (dimethyl carbonate), and taking a diaphragm as a Lelgard2400 membrane, and filling a glove box filled with argon atmosphere into a CR2025 button cell;
(5) as shown in fig. 4, the battery manufactured according to the present embodiment has a first charge specific capacity of 1768mAh/g, a first discharge specific capacity of 1415mAh/g, a second charge specific capacity of 1502.8mAh/g, and a second discharge specific capacity of 1203mAh/g, which mainly includes a solid electrolyte film (SEI) film generated during the first discharge process and a partial irreversible reaction, such as a part of carbon uncoated flocculent elemental silicon nanowire coil/carbon composite negative electrode material, which cracks and falls off due to a small amount of oxygen in the composite material being combined with lithium to generate lithium oxide. However, the specific capacity attenuation of the battery is not obvious along with the increase of the cycle times after the first charging and discharging, and the discharge capacity is still kept at 1118mAh/g after 100 cycles, which shows that the carbon shell of the cotton flocculent elemental silicon nanowire coil/carbon composite material effectively inhibits the volume expansion effect of silicon and improves the cycle performance of the lithium ion battery.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (6)
1. A preparation method of cotton-shaped flocculent elemental silicon nanowire coils is characterized by comprising the following steps: (1) putting high-purity silicon with the purity of 98-99.9999% into a reactor in a steam reaction furnace, heating the high-purity silicon into gaseous high-purity silicon by using a plasma spray gun in the reactor under the condition of a vacuum closed environment, feeding the gaseous high-purity silicon into a growth controller through a pipeline to grow into cotton flocculent elemental silicon nano-wire clusters with controlled sizes, feeding the cotton flocculent elemental silicon nano-wire clusters and gas in the reactor into a collector through the pipeline together, carrying out gas-solid separation to obtain solid cotton flocculent elemental silicon nano-wire clusters, communicating a vacuum pump, an exhaust fan and a heat exchanger on the pipeline communicated with a gas outlet of the collector, communicating cooling gas passing through the heat exchanger with an inner cavity of the reactor through the reaction furnace, and communicating a discharge port of a storage barrel and a feed pipe of the growth controller with the inner cavity of the reactor through the reactor; the feeding pipeline at the front part of the growth controller is a front feeding pipe, the discharging pipeline at the rear part is a rear discharging pipe, and the ratio of the length of the front feeding pipe to the inner diameter of the growth controller is (0.1-10): 1, the ratio of the inner diameter of the front feeding pipe to the inner diameter of the growth controller is (0.05-0.8): 1; controlling the conglomeration size of the cotton flocculent elemental silicon nanowire clusters by controlling the flow, the flow direction and the cooling speed of the materials entering and exiting the growth controller, thereby obtaining the required cotton flocculent elemental silicon nanowire clusters; (2) opening a discharge valve port of the collector, and taking out the cotton flocculent elemental silicon nanowire clusters; the purity of the cotton-shaped simple substance silicon nanowire cluster is 98-99.9999%.
2. A preparation method of a cotton-shaped single substance silicon nanowire cluster/carbon composite anode material is characterized by comprising the following steps: the method comprises the following steps: (1) preparing a polymer solution: weighing the flocculent elemental silicon nanowire clusters and the medium and high molecular polymer prepared by the method of claim 1, wherein the elemental silicon nanowire clusters account for 10-90% by mass, the medium and high molecular polymer accounts for 10-90% by mass, and the weighed medium and high molecular polymer is dissolved in a solvent to obtain a polymer solution with the weight of 1-30 wt%; (2) primary mixing: filling the flocculent elemental silicon nanowire clusters weighed in the step (1) into the medium-high molecular polymer solution prepared in the step (1), and performing mechanical stirring, uniform dispersing and mixing, or mechanical emulsifying, dispersing and mixing, or ultrasonic uniform dispersing and mixing to obtain a mixed solution; (3) secondary mixing: pumping the mixed solution prepared in the step (2) to a pressure container with the temperature of 150-; (4) filtering and baking: filtering or baking the uniform mixed solution prepared in the step (3) by using a solvent or baking the uniform mixed solution after filtering or baking the uniform mixed solution to obtain a mixture material; (5) carbonizing: putting the mixture material prepared in the step (4) into a material boat, putting the material boat into a heating reaction furnace, baking and heating the material to the temperature of 900-1600 ℃ under the protection of nitrogen and/or inert gas, preserving the heat for 2-24 hours, carrying out carbonization reaction on the mixture material, naturally cooling the material to the temperature below 200 ℃, taking out the material after the carbonization reaction, and crushing and sieving the material to obtain the cotton flocculent elemental silicon nano coil/carbon composite cathode material;
the polymer is one or more of the following materials: phenolic resin, asphalt, glucose, sucrose, starch, polyacrylonitrile, polymethyl methacrylate and polyvinyl chloride.
3. The preparation method of the cotton flocculent elemental silicon nanowire cluster/carbon composite anode material according to claim 2, characterized in that: the reaction furnace is one of a vacuum tube furnace, a rotary furnace, a roller kiln and a push plate kiln; the inert gas is one or more of neon, argon and helium.
4. A battery negative electrode for a lithium battery, characterized by: the negative electrode comprises the cotton flocculent elemental silicon nanowire cluster/carbon composite negative electrode material prepared by the preparation method of the cotton flocculent elemental silicon nanowire cluster/carbon composite negative electrode material as claimed in any one of claims 2 to 3.
5. A lithium battery, characterized in that: the lithium battery comprises a battery positive electrode, a battery negative electrode, an electrolyte and a separator, wherein the battery negative electrode is the battery negative electrode of the lithium battery as claimed in claim 4;
the battery made of the obtained cotton-shaped single substance silicon nanowire roll/carbon composite negative electrode material has the specific first charge capacity of more than 1768mAh/g, the specific first discharge capacity of more than 1415mAh/g, the discharge capacity after 100 cycles is kept at more than 1118mAh/g, and the attenuation rate is below 36.76%.
6. The cotton-shaped elemental silicon nanowire cluster/carbon composite anode material prepared by the preparation method of the cotton-shaped elemental silicon nanowire cluster/carbon composite anode material as claimed in any one of claims 2 to 3, is characterized in that: the elemental silicon nanowire cluster is of a cotton-shaped structure formed by integrating elemental silicon nanowires or elemental silicon nanoparticles and elemental silicon nanowires, wherein conductive carbon materials or mixed conductive materials are coated on the outer surface of the elemental silicon nanowire cluster and in gaps of the elemental silicon nanowire cluster to form a lithium ion battery cathode material; in the structure of the elemental silicon nanowire cluster, the mass of the elemental silicon nanowire with the diameter of 15nm-300nm accounts for more than 50% of the total mass of the elemental silicon nanowire cluster; in the structure of the elemental silicon nanowire clusters, the mass of the elemental silicon nanowire clusters with the diameter of 0.5-100 mu m accounts for more than 50% of the total mass of the elemental silicon nanowire clusters; the conductive carbon material is formed by carbonizing a medium-high molecular polymer selected from the following polymers: phenolic resin, asphalt, glucose, sucrose, starch, polyacrylonitrile, polymethyl methacrylate and polyvinyl chloride.
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