CN114122370A - Negative electrode material for inducing silane deposition through porous carbon double bond modification and preparation method and application thereof - Google Patents
Negative electrode material for inducing silane deposition through porous carbon double bond modification and preparation method and application thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 133
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 48
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 44
- 230000008021 deposition Effects 0.000 title claims abstract description 26
- 230000001939 inductive effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000004048 modification Effects 0.000 title claims description 20
- 238000002715 modification method Methods 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000004005 microsphere Substances 0.000 claims abstract description 95
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- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims description 31
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- 238000002156 mixing Methods 0.000 claims description 19
- 238000012986 modification Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
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- 230000006698 induction Effects 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052710 silicon Inorganic materials 0.000 abstract description 14
- 239000010703 silicon Substances 0.000 abstract description 14
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 10
- 239000006257 cathode slurry Substances 0.000 description 10
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a porous carbon double bond modified silane deposition-induced negative electrode material and a preparation method thereof. The porous carbon microsphere is composed of conductive carbon black (SP) and Carbon Nano Tubes (CNT), and silicon particles are uniformly attached to the inside or the surface of the porous carbon microsphere. The invention provides a method for preparing a silicon-carbon negative electrode material by modifying and inducing silane deposition with porous carbon double bonds, aiming at the defects in the prior art, based on the characteristics of carbon material such as conductivity, protectiveness, mechanical strength, cycling stability, abundant sources and low cost, and comprehensively considering the high specific volume of silicon as a main material and the high conductivity and protectiveness of the carbon material.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a negative electrode material for inducing silane deposition by modifying porous carbon double bonds, and a preparation method and application thereof.
Background
With the rapid development of the global economic era since the 21 st century, energy problems have become one of the most prominent problems facing human society. The lithium ion battery has the advantages of high energy power density, high working voltage, good safety, environmental protection and the likeThe method is widely applied to the fields of mobile phones, notebook computers, new energy automobiles and the like. The lithium ion battery with high specific energy is bound to move from electronic terminal equipment to electric automobiles and the technical field of energy storage. However, the current commercialized lithium ion battery cathode material is mainly made of graphite, and the capacity exertion of the lithium ion battery cathode material is close to the theoretical capacity (372mA h g)-1) And the improvement is difficult to be realized, so that the research and development of the cathode material with high specific energy are of great significance.
Silicon element due to its natural abundance, environmental friendliness, relatively low lithiation potential (ii)<0.4V vs Li/Li+) And 4200mA h g-1The high theoretical specific capacity (more than 10 times of that of the traditional graphite cathode) is recognized as one of the most attractive cathode material candidates in the next generation of lithium ion batteries. However, commercialization of silicon-based anodes is limited to three areas: (1) the huge volume change in the charge-discharge cycle process can induce the internal stress of the electrode to accumulate and generate cracks, so that the electrode is pulverized, and the active material is separated from the current collector, thereby attenuating the performance; (2) a solid electrolyte interface film (SEI) can be repeatedly cracked and regenerated along with the volume expansion and contraction of silicon, active lithium is continuously consumed to cause battery polarization, and the cycle stability is reduced; (3) the conductivity of silicon is poor, and the release of battery capacity is not facilitated under large current.
The existing improvement technology comprises nanocrystallization, and silicon is made into nanospheres, nanowires, nanotubes and the like, so that the expansion of silicon in the circulation process can be relieved to a certain extent, and the circulation stability is improved. However, excessive nanocrystallization causes silicon particles to have large surface energy, secondary agglomeration is easy to form particles, and the large specific surface area of nano silicon consumes excessive lithium ions to reduce the coulombic efficiency of the battery, so that the nano silicon is difficult to be suitable for use of a commercial negative electrode material. In addition, the preparation process of the nano silicon is complex, and the preparation cost is high, so that the nano silicon is difficult to produce on a large scale. Therefore, the material which can simultaneously solve the silicon-based volume expansion effect and the conductivity is designed and synthesized, and the low-cost and high-efficiency preparation method applied in a large scale has important value.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a negative electrode material for inducing silane deposition by modifying porous carbon double bonds and a preparation method thereof, so as to solve the problems of unstable cycle, poor conductivity and low first effect caused by nano-silicon agglomeration in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a negative electrode material for inducing silane deposition by modifying porous carbon double bonds comprises porous carbon microspheres, wherein a plurality of holes are formed in the porous carbon microspheres; silicon particles, conductive carbon black Super P and carbon nano tubes are embedded in the porous carbon microspheres.
The invention is further improved in that:
preferably, the mass ratio of the porous carbon microspheres to the silicon particles is (2-5): (8-5).
Preferably, the equivalent diameter of the porous carbon microsphere is 10 um-50 um.
A preparation method of a negative electrode material for inducing silane deposition by porous carbon double bond modification comprises the following steps:
step 1, mixing a binder, conductive carbon black Super P, a carbon nano tube, PVP polyvinylpyrrolidone and water, and emulsifying to obtain a mixed solution a;
step 3, heat treating the porous carbon microspheres;
and 4, adding the porous carbon microspheres subjected to heat treatment and a double-bond silane coupling agent into strong acid, performing hydrothermal reaction to obtain double-bond modified porous carbon microspheres, placing the double-bond modified porous carbon microspheres in a closed container, and introducing silane gas into the closed container to obtain the negative electrode material.
Preferably, in the step 1, the mass ratio of the binder, the conductive carbon black Super P and the carbon nano tube is (25-77): (19.2-62.5): (3.8-12.5).
Preferably, in the step 1, the mass ratio of the total mass of the binder, the conductive carbon black Super P and the carbon nano tubes to the mass of water is (5-10): (90-95).
Preferably, in step 1, the binder is melamine formaldehyde resin or phenolic resin.
Preferably, in the step 2, the inlet temperature of the spray drying fan is set to be 75-85 ℃.
Preferably, in the step 4, the hydrothermal reaction temperature is 70 ℃ and the hydrothermal reaction time is 6-8 hours.
Preferably, in the step 4, silane gas is introduced into the closed container, and the temperature is kept for 90 min.
The application of the negative electrode material for inducing silane deposition by porous carbon double bond modification in a lithium battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a negative electrode material for inducing silane deposition by modifying porous carbon double bonds. The porous carbon microsphere is composed of conductive carbon black (SP) and Carbon Nano Tubes (CNT), and silicon particles are uniformly attached to the inside or the surface of the porous carbon microsphere. The invention provides a method for preparing a silicon-carbon negative electrode material by modifying and inducing silane deposition with porous carbon double bonds, aiming at the defects in the prior art, based on the characteristics of carbon material such as conductivity, protectiveness, mechanical strength, cycling stability, abundant sources and low cost, and comprehensively considering the high specific volume of silicon as a main material and the high conductivity and protectiveness of the carbon material.
The invention also discloses a preparation method of the porous carbon double-bond modified silane deposition-induced negative electrode material, which comprises the steps of firstly preparing a precursor of the porous carbon microsphere through conductive carbon black and a carbon nano tube, carrying out spray drying treatment on the porous carbon microsphere, then carrying out heat treatment on the porous carbon microsphere, adding the porous carbon microsphere into strong acid, carrying out hydrothermal reaction to prepare the double-bond modified porous carbon microsphere, introducing silane gas, and embedding silicon particles into the porous carbon microsphere along with the cracking of the silane gas.
The invention also discloses application of the negative electrode material for inducing silane deposition by modifying porous carbon double bonds in a lithium battery, the negative electrode material has the advantages of high specific volume of silicon as a main material, excellent carbon material conductivity, certain mechanical strength and low cost, and the three-dimensional porous carbon micro-porous carbon is prepared by spray drying granulation and carbon-carbon double bond modification induction silane depositionThe ball adsorbs the composite material of silicon particle. Compared with a simple mechanically-mixed silicon-carbon cathode, the three-dimensional porous spherical structure and the close bonding of the main silicon-based material and the porous carbon microspheres as the matrix material not only improve the conductivity of the silicon-carbon composite material and accommodate the volume expansion of silicon in the lithium embedding process, but also facilitate the transmission of lithium ions due to the close bonding effect, so that the silicon-based materials are uniformly dispersed and not easy to aggregate, thereby stabilizing the structure of the electrode and improving the rate capability and the cycling stability of the battery. The material is used as a lithium ion battery cathode material, has a simple preparation method, has high initial discharge capacity, first charge-discharge efficiency and cycle stability, and has a very wide application prospect. When the composite material prepared by the method for inducing silane deposition by modifying porous carbon double bonds is used as a lithium ion battery cathode material, the first charge-discharge efficiency and the charge-discharge cycle performance are obviously improved, and the concrete expression is as follows: with the increase of the number of the circulation circles, the capacity of the battery is still kept stable, and the first discharge capacity is 1755mA h g at 0.1C-1～3270mA hg-1The first charge-discharge efficiency reaches 85-91%.
Drawings
FIG. 1 is a scanning electron microscope photograph of a three-dimensional porous conductive carbon microsphere prepared in example 1;
wherein: (a) is SEM image of three-dimensional conductive carbon microsphere;
(b) SEM images of porous, three-dimensional conductive networks formed for conductive carbon spheres;
FIG. 2 is an SEM photograph of the silicon-carbon anode material obtained in example 1;
FIG. 3 is an SEM image of three-dimensional porous conductive carbon microspheres prepared in example 7;
wherein: (a) is SEM picture of three-dimensional porous conductive carbon microsphere;
(b) is an SEM image of the composition of the porous carbon microspheres and silicon;
fig. 4 is a specific cycle discharge capacity (a) and a charge-discharge efficiency (b) of the silicon-carbon negative electrode material obtained in example 1;
fig. 5 is a specific cycle discharge capacity (a) and a charge-discharge efficiency (b) of the silicon-carbon negative electrode material obtained in example 4;
fig. 6 is a specific cycle discharge capacity (a) and a charge-discharge efficiency (b) of the silicon-carbon negative electrode material obtained in example 5;
FIG. 7 is a schematic structural diagram of a silicon-carbon material obtained by modification of porous carbon double bonds to induce silane deposition;
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the method comprises the following steps: mixing a specific binder, a conductive agent and a dispersant with water, and emulsifying to obtain a mixed solution a. The dispersant is PVP polyvinylpyrrolidone.
The binder is any one of melamine formaldehyde resin and phenolic resin; the conductive agent is a composite conductive agent composed of conductive carbon black Super P and Carbon Nano Tubes (CNT). The carbon nano tube in the conductive agent has good conductivity and can be used for forming a three-dimensional conductive network in a sphere, and the conductive carbon black SP is beneficial to forming a skeleton structure.
The mass ratio of the binder, the conductive carbon black Super P and the carbon nano tube is (25-77): (62.5-19.2): (12.5-3.8).
The ratio of the total mass of the binder, the conductive agent and the dispersing agent to water is (5-10): (95-90), wherein the emulsifying time is 20 minutes.
Step two: and granulating the mixed solution a by adopting a spray drying method to obtain the porous carbon microspheres. The spray drying method can enable the water in the mixed solution a to be instantly volatilized and sprayed out under a large pressure, and is favorable for forming a spherical porous structure.
The experimental parameters of the spray drying are as follows: setting a fan (75-85 ℃); the inlet (wind) temperature is set to 200 ℃; and (4) setting the outlet temperature to be 120-130 ℃, and determining the drying time according to the dosage of the mixed solution a until the porous carbon microspheres are obtained, wherein the spherical shape and the moisture are required to be fully removed.
Step three: and carrying out heat treatment on the obtained porous carbon microspheres, wherein the heat treatment temperature is 900-1100 ℃, the heat treatment time is 3 hours, argon is used as a protective atmosphere in the heat treatment process, and the binder influencing the conductivity can be sufficiently removed through the heat treatment temperature and time.
Step four: performing surface and internal modification of double bonds on the porous carbon microspheres by adopting a hydrothermal synthesis and stirring method, placing the porous carbon microspheres in a closed container, introducing silane gas, adsorbing the silane gas on the surfaces and the interiors of the porous carbon microspheres, and performing pyrolysis to obtain the composite material with silicon particles uniformly adsorbed on the porous carbon microspheres.
Further, the preparation steps of the porous carbon microsphere modified double bond and the composite material comprise: adding the heat-treated porous carbon microspheres and the double-bond silane coupling agent into a reaction kettle, wherein the mass ratio of the porous carbon microspheres to the double-bond silane coupling agent is 3: 10; then adding strong acid, wherein the strong acid is mixed acid of concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1), placing the reaction kettle in a drying oven for hydrothermal reaction at 70 ℃ for 6-8 hours, and centrifugally cleaning and drying a reaction product to obtain modified porous carbon microspheres; and (3) placing the modified porous carbon microspheres in a sealed container after gas washing, introducing high-purity silane into the container, raising the temperature to 310 ℃, and preserving the temperature for 90 minutes to ensure that the silane can be fully cracked. The mass ratio of the porous carbon microspheres to the silicon particles subjected to silane cracking is (2-5): (8-5), and the proportion ensures that the structure of the whole microsphere is stable. After this in-process porous carbon microsphere and strong acid hydrothermal reaction, because oxidation for porous carbon microsphere surface contains a large amount of oxygen functional groups (hydroxyl), with silane coupling agent reaction back, double bond silane coupling agent is the porous carbon microsphere modification double bond, and the double bond more is favorable to inducing the silane deposit, silane coupling agent for connecting the bridge of the adsorbed silicon granule behind carbon microsphere and the silane schizolysis, silicon granule after the silane schizolysis adsorbs on the porous carbon microsphere.
Referring to fig. 7, the finally prepared negative electrode material includes porous carbon microspheres, silicon particles are embedded in the porous carbon microspheres, and carbon nanotubes are embedded in the porous carbon microspheres.
The invention also provides a lithium ion battery which consists of a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the negative electrode material is a silicon-carbon composite material prepared by the porous carbon double bond modification induced silane deposition.
The present invention is described in further detail below with reference to specific examples:
example 1
Mixing melamine formaldehyde resin (MF), conductive carbon black Super P and carbon nano tubes in a weight ratio of 25: 62.5: 12.5, wherein the solid content is 5% (the solid content is the total mass sum of the binder, the conductive agent and the dispersing agent), and the water content is 95%. Emulsifying the mixed solution with emulsifying machine for 20min, spray granulating at 75 deg.C, 200 deg.C and 120 deg.C to obtain porous carbon spheres, and heat treating in 1100 deg.C tube furnace for 3 hr. Adding the heat-treated porous carbon microspheres, concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) into a reaction kettle, placing the mixture into a drying oven to react for 8 hours, wherein the hydrothermal reaction temperature is 70 ℃, and centrifugally cleaning and drying to obtain modified porous carbon microspheres; and then placing the silicon carbide anode material in a sealed container after gas washing, introducing high-purity silane, raising the temperature to 310 ℃, and preserving the temperature for 90 minutes to obtain the silicon carbide anode material, wherein the mass ratio of the porous carbon microspheres to the silicon particles is 3: 7. Mixing a negative electrode material, a conductive agent and a binder in a weight ratio of 80: 10: 10, ball-milling in a planetary ball mill to obtain uniformly dispersed cathode slurry; and coating, vacuum drying to obtain the final electrode.
Fig. 1 is a scanning electron microscope image of the three-dimensional porous conductive carbon microsphere prepared in this embodiment, and it can be seen from fig. 1 that the microsphere is uniformly distributed, has a size of 10um to 50um, and exhibits a three-dimensional conductive network and a clear porous structure.
Fig. 2 shows the final preparation of the silicon-carbon composite material with silicon particles adsorbed by porous carbon double bond modification in this example. As can be seen from fig. 2, the adsorbed silicon particles are uniformly distributed on the porous carbon spheres.
Mixing a negative electrode material, a conductive agent and a binder in a weight ratio of 80: 10: 10, ball-milling in a planetary ball mill to obtain uniformly dispersed cathode slurry; and coating the copper foil current collector, and drying in vacuum to obtain the final electrode. The silicon-carbon composite electrode is transferred into a super-purification glove box filled with argon to assemble a 2032 type button half-cell for testing, and the result shows that the charge-discharge performance of the silicon-carbon cathode prepared by the method is obviously obtained under the multiplying power of 0.1C and the multiplying power of figure 4The improvement is represented by the specific capacity of initial discharge of 2126mA h g-1First coulombic efficiency 86%. The capacity of the battery after 50 cycles is kept stable with the increase of the cycle times under the 0.5C multiplying power.
Example 2
Melamine formaldehyde resin (MF), conductive carbon black Super P, carbon nano-tube with the weight ratio of 50: 41.7: 8.3, wherein the solid content is 5 percent (the solid content is the total mass sum of the binder, the conductive agent and the dispersant), and the water content is 95 percent. Emulsifying the mixed solution with emulsifying machine for 20min, spray granulating at 80 deg.C, 200 deg.C and 120 deg.C to obtain porous carbon spheres, and heat treating in 1100 deg.C tube furnace for 3 hr. Adding the heat-treated porous carbon microspheres, concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) into a reaction kettle, placing the mixture into a drying oven to react for 8 hours at the reaction temperature of 70 ℃, and centrifugally cleaning and drying to obtain modified porous carbon microspheres; and then placing the silicon carbide anode material in a sealed container after gas washing, introducing high-purity silane, raising the temperature to 310 ℃, and preserving the temperature for 90 minutes to obtain the silicon carbide anode material, wherein the mass ratio of the porous carbon microspheres to the silicon particles is 3: 7.
Mixing a negative electrode material, a conductive agent and a binder in a weight ratio of 80: 10: 10, ball-milling in a planetary ball mill to obtain uniformly dispersed cathode slurry; and coating, vacuum drying to obtain the final electrode. The silicon-carbon composite electrode is transferred into a super-purification glove box filled with argon to assemble a 2032 type button half-cell for testing, and the result shows that the charge-discharge performance of the silicon-carbon cathode prepared by the method provided by the invention under the 0.1C multiplying power is obviously improved, and the specific initial discharge capacity is 2626mA hg-1The first coulombic efficiency was close to 90%. The capacity of the battery after 50 cycles is kept stable with the increase of the cycle times under the 0.5C multiplying power.
Example 3
Mixing melamine formaldehyde resin (MF), conductive carbon black Super P and carbon nano tubes in a weight ratio of 25: 62.5: 12.5 with a solid content of 5% (solid content is the sum of the total mass of the binder, the conductive agent and the dispersant) and a water content of 95%, emulsifying the mixed solution with an emulsifying machine for 20min, performing spray granulation with a blower set at 85 ℃, an inlet temperature set at 200 ℃ and an outlet temperature set at 130 ℃ to obtain porous carbon spheres, and performing heat treatment in a 1100 ℃ tube furnace for 3 hours. Adding the heat-treated porous carbon microspheres, concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) into a reaction kettle, placing the mixture into a drying oven to react for 8 hours at the reaction temperature of 70 ℃, and centrifugally cleaning and drying to obtain modified porous carbon microspheres; and then placing the porous carbon microspheres in a sealed container after gas washing, introducing high-purity silane, raising the temperature to 310 ℃, and preserving the temperature for 90 minutes to obtain the porous carbon microspheres with the mass ratio of 2: 8 silicon carbon negative electrode material.
Mixing a negative electrode material, a conductive agent and a binder in a weight ratio of 80: 10: 10, ball-milling in a planetary ball mill to obtain uniformly dispersed cathode slurry; and coating, vacuum drying to obtain the final electrode. Initial discharge specific capacity of 2977mA h g under 0.1C multiplying power-1First coulombic efficiency 90.4%.
Example 4
Melamine formaldehyde resin (MF), conductive carbon black Super P, carbon nano-tube with a weight ratio of 77: 19.2: 3.8, wherein the solid content is 5 percent (the solid content is the total mass of the binder, the conductive agent and the dispersing agent) and the water content is 95 percent, emulsifying the mixed solution by using an emulsifying machine for 20min, carrying out spray granulation under the conditions that a fan is set to be 75 ℃, the inlet temperature is set to be 200 ℃ and the outlet temperature is set to be 130 ℃ to obtain porous carbon balls, and then placing the porous carbon balls in a 1100 ℃ tube furnace for heat treatment for 3 hours. Adding the heat-treated porous carbon microspheres, concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) into a reaction kettle, placing the mixture into a drying oven to react for 8 hours at the reaction temperature of 70 ℃, and centrifugally cleaning and drying to obtain modified porous carbon microspheres; and then placing the porous carbon microspheres in a sealed container after gas washing, introducing high-purity silane, raising the temperature to 310 ℃, and preserving the temperature for 90 minutes to obtain the porous carbon microspheres with the mass ratio of 3:7 silicon carbon cathode material.
Mixing a negative electrode material, a conductive agent and a binder in a weight ratio of 80: 10: 10, ball-milling in a planetary ball mill to obtain uniformly dispersed cathode slurry; and coating, vacuum drying to obtain the final electrode. Transferring the silicon-carbon composite electrode into a super-purification glove box filled with argon to assemble a 2032 type button half cellThe test result is shown in figure 5, the charge and discharge performance of the silicon-carbon cathode prepared by the method is obviously improved under the multiplying power of 0.1C, and the specific capacity of initial discharge is 3270mA h g-1First coulombic efficiency 89.4%. The capacity of the battery after 50 cycles is kept stable with the increase of the cycle times under the 0.5C multiplying power.
Example 5
Melamine formaldehyde resin (MF), conductive carbon black Super P, carbon nanotubes in a weight ratio of 37.5: 50: 12.5 with a solid content of 5% (solid content is the sum of the total mass of the binder, the conductive agent and the dispersant) and a water content of 95%, emulsifying the mixed solution with an emulsifying machine for 20min, performing spray granulation with a blower set at 75 ℃, an inlet temperature set at 200 ℃ and an outlet temperature set at 120 ℃ to obtain porous carbon spheres, and performing heat treatment in a 1100 ℃ tube furnace for 3 hours. Adding the heat-treated porous carbon microspheres, concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) into a reaction kettle, placing the mixture into a drying oven to react for 8 hours at the reaction temperature of 70 ℃, and centrifugally cleaning and drying to obtain modified porous carbon microspheres; and then placing the mixture in a sealed container after gas washing, introducing high-purity silane, raising the temperature to 310 ℃, and preserving the temperature for 90 minutes to obtain the silicon-carbon porous carbon microspheres with the mass ratio of 3:7 negative electrode material.
Mixing a negative electrode material, a conductive agent and a binder in a weight ratio of 80: 10: 10, ball-milling in a planetary ball mill to obtain uniformly dispersed cathode slurry; and coating, vacuum drying to obtain the final electrode. The silicon-carbon composite electrode is transferred into a super-purification glove box filled with argon to assemble a 2032 type button half-cell for testing, and the result is shown in figure 6, the charge and discharge performance of the silicon-carbon cathode prepared by the method is obviously improved under the multiplying power of 0.1C, and the specific initial discharge capacity is 2992mA h g-1The first coulombic efficiency was 87.8%. The capacity of the battery after 50 cycles is kept stable with the increase of the cycle times under the 0.5C multiplying power.
Example 6
Mixing melamine formaldehyde resin (MF), conductive carbon black Super P and carbon nano tubes in a weight ratio of 25: 62.5: 12.5, wherein the solid content is 5 percent, then emulsifying the mixed solution for 20min by an emulsifying machine,spray granulation was performed with a blower set to 80 ℃, an inlet temperature set to 200 ℃, and an outlet temperature set to 130 ℃ to obtain porous carbon spheres, which were then heat-treated in a 1100 ℃ tube furnace for 3 hours. Adding the heat-treated porous carbon microspheres, concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) into a reaction kettle, placing the mixture into a drying oven to react for 7 hours at the reaction temperature of 70 ℃, and centrifugally cleaning and drying to obtain modified porous carbon microspheres; and then placing the porous carbon microspheres in a sealed container after gas washing, introducing high-purity silane, raising the temperature to 310 ℃, and preserving the temperature for 90 minutes to obtain the porous carbon microspheres with the mass ratio of 5: 5 silicon carbon cathode material. Mixing a negative electrode material, a conductive agent and a binder in a weight ratio of 80: 10: 10, ball-milling in a planetary ball mill to obtain uniformly dispersed cathode slurry; and coating, vacuum drying to obtain the final electrode. At 0.1C multiplying power, the initial discharge specific capacity is 2825mA h g-1The first coulombic efficiency was 85.6%. The capacity of the battery after 50 cycles is kept stable with the increase of the cycle times under the 0.5C multiplying power.
Example 7
Mixing phenolic resin (PF), conductive carbon black Super P and carbon nano tubes in a weight ratio of 25: 62.5: 12.5 with a solid content of 5% (solid content is the sum of the total mass of the binder, the conductive agent and the dispersant) and a water content of 95%, emulsifying the mixed solution with an emulsifying machine for 20min, performing spray granulation with a blower set at 75 ℃, an inlet temperature set at 200 ℃ and an outlet temperature set at 120 ℃ to obtain porous carbon spheres, and performing heat treatment in a 1100 ℃ tube furnace for 3 hours. Adding the heat-treated porous carbon microspheres, concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) into a reaction kettle, placing the mixture into a drying oven to react for 8 hours at the reaction temperature of 70 ℃, and centrifugally cleaning and drying to obtain modified porous carbon microspheres; and then placing the porous carbon microspheres in a sealed container after gas washing, introducing high-purity silane, raising the temperature to 310 ℃, and preserving the temperature for 90 minutes to obtain the porous carbon microspheres with the mass ratio of 3:7 silicon carbon cathode material. Mixing a negative electrode material, a conductive agent and a binder in a weight ratio of 80: 10: 10, ball-milling in a planetary ball mill to obtain uniformly dispersed cathode slurry; and coating, vacuum drying to obtain the final electrode.
Fig. 3(a) is a scanning electron microscope image of the three-dimensional porous conductive carbon microsphere prepared in this embodiment, and it can be seen from the image that the microsphere is distributed uniformly, and has a size of 10um to 50um, and exhibits a three-dimensional conductive network and a clear porous structure.
Fig. 3(b) shows the finally prepared silicon-carbon composite material with silicon particles adsorbed by porous carbon double bond modification in this example. As can be seen from the figure, the adsorbed silicon particles are uniformly distributed on the porous carbon spheres.
Example 8
Mixing melamine formaldehyde resin (MF), conductive carbon black Super P and carbon nano tubes in a weight ratio of 25: 62.5: 12.5 with a solid content of 10% (solid content is the sum of the total mass of the binder, the conductive agent and the dispersant) and a water content of 90%, emulsifying the mixed solution with an emulsifying machine for 20min, performing spray granulation with a blower set at 80 ℃, an inlet temperature set at 200 ℃ and an outlet temperature set at 130 ℃ to obtain porous carbon spheres, and performing heat treatment in a 900 ℃ tube furnace for 3 hours. Adding the heat-treated porous carbon microspheres, concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) into a reaction kettle, placing the mixture in an oven for reaction for 6 hours at the reaction temperature of 70 ℃, and centrifugally cleaning and drying to obtain modified porous carbon microspheres; and then placing the porous carbon microspheres in a sealed container after gas washing, introducing high-purity silane, raising the temperature to 310 ℃, and preserving the temperature for 90 minutes to obtain porous carbon microspheres with the mass ratio of 4: 6 silicon carbon cathode material. Mixing a negative electrode material, a conductive agent and a binder in a weight ratio of 80: 10: 10, ball-milling in a planetary ball mill to obtain uniformly dispersed cathode slurry; and coating, vacuum drying to obtain the final electrode.
Example 9
Mixing melamine formaldehyde resin (MF), conductive carbon black Super P and carbon nano tubes in a weight ratio of 25: 62.5: 12.5 with a solid content of 8% (solid content is the sum of the total mass of the binder, the conductive agent and the dispersant) and a water content of 92%, emulsifying the mixed solution with an emulsifying machine for 20min, performing spray granulation with a blower set at 85 ℃, an inlet temperature set at 200 ℃ and an outlet temperature set at 130 ℃ to obtain porous carbon spheres, and performing heat treatment in a 1000 ℃ tube furnace for 3 hours. Adding the heat-treated porous carbon microspheres, concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) into a reaction kettle, placing the mixture into a drying oven to react for 7 hours at the reaction temperature of 70 ℃, and centrifugally cleaning and drying to obtain modified porous carbon microspheres; and then placing the porous carbon microspheres in a sealed container after gas washing, introducing high-purity silane, raising the temperature to 310 ℃, and preserving the temperature for 90 minutes to obtain the porous carbon microspheres with the mass ratio of 5: 5 silicon carbon cathode material. Mixing a negative electrode material, a conductive agent and a binder in a weight ratio of 80: 10: 10, ball-milling in a planetary ball mill to obtain uniformly dispersed cathode slurry; and coating, vacuum drying to obtain the final electrode.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A negative electrode material for inducing silane deposition by modifying porous carbon double bonds is characterized by comprising porous carbon microspheres, wherein a plurality of holes are formed in the porous carbon microspheres; silicon particles, conductive carbon black Super P and carbon nano tubes are embedded in the porous carbon microspheres.
2. The negative electrode material for silane deposition induction through modification of porous carbon double bonds, according to claim 1, is characterized in that the mass ratio of the porous carbon microspheres to the silicon particles is (2-5): (8-5).
3. The negative electrode material for silane deposition induction through modification of porous carbon double bonds, according to claim 1, is characterized in that the equivalent diameter of the porous carbon microspheres is 10-50 um.
4. A preparation method of a negative electrode material for inducing silane deposition by porous carbon double bond modification is characterized by comprising the following steps:
step 1, mixing a binder, conductive carbon black Super P, a carbon nano tube, PVP polyvinylpyrrolidone and water, and emulsifying to obtain a mixed solution a;
step 2, treating the mixed solution a through spray drying to prepare porous carbon microspheres;
step 3, heat treating the porous carbon microspheres;
and 4, adding the porous carbon microspheres subjected to heat treatment and a double-bond silane coupling agent into strong acid, performing hydrothermal reaction to obtain double-bond modified porous carbon microspheres, placing the double-bond modified porous carbon microspheres in a closed container, and introducing silane gas into the closed container to obtain the negative electrode material.
5. The preparation method of the negative electrode material for inducing silane deposition through porous carbon double bond modification according to claim 4, wherein in the step 1, the mass ratio of the binder to the conductive carbon black Super P to the carbon nanotubes is (25-77): (19.2-62.5): (3.8-12.5).
6. The preparation method of the negative electrode material for inducing silane deposition through porous carbon double bond modification according to claim 4, wherein in the step 1, the mass ratio of the total mass of the binder, the conductive carbon black Super P and the carbon nano tubes to the mass of water is (5-10): (90-95).
7. The method for preparing the negative electrode material for inducing silane deposition through porous carbon double bond modification according to claim 4, wherein in the step 1, the binder is melamine formaldehyde resin or phenolic resin.
8. The preparation method of the negative electrode material for inducing silane deposition through porous carbon double bond modification according to claim 4, wherein in the step 2, the inlet temperature of a fan for spray drying is set to be 75-85 ℃.
9. The preparation method of the negative electrode material for silane deposition induced by porous carbon double bond modification according to claim 4, wherein in the step 4, the hydrothermal reaction temperature is 70 ℃, and the hydrothermal reaction time is 6-8 hours;
and 4, introducing silane gas into the closed container, and preserving the heat for 90 min.
10. The application of the negative electrode material which is obtained by modifying the porous carbon double bond and inducing silane deposition and is disclosed in claim 1 in a lithium battery.
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