CN116005030A - Cobalt-based composite material, preparation method and application thereof - Google Patents
Cobalt-based composite material, preparation method and application thereof Download PDFInfo
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- 238000007740 vapor deposition Methods 0.000 claims abstract description 15
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 7
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- 239000001301 oxygen Substances 0.000 claims description 7
- 239000011669 selenium Substances 0.000 claims description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000013077 target material Substances 0.000 claims description 6
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- 229910021382 natural graphite Inorganic materials 0.000 claims description 5
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- 229910001416 lithium ion Inorganic materials 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
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- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention provides a cobalt-based composite material, a preparation method and application thereof. The preparation method comprises the following steps: s1, coSb 3 And (3) carrying out spark plasma sintering treatment on the mixed powder of the cobalt-based composite material and graphitized carbon, then carrying out ball milling treatment to obtain an alloy precursor material S2, taking the alloy precursor material as a matrix, and depositing a non-metal semiconductor material layer on the matrix by utilizing an atomic vapor deposition method to obtain the cobalt-based composite material. The cobalt-based composite material obtained by the preparation method is very suitable to be used as a lithium ion battery negative electrode material, and can effectively improve the battery capacity and improve the battery cycle performance.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to a cobalt-based composite material, a preparation method and application thereof.
Background
For lithium ion batteries, the mainstream negative electrode material graphite material cannot meet the increasing energy density requirement due to the relatively low theoretical specific capacity (372 mAh/g). Therefore, a precondition for further application to lithium ion batteries is the preparation of negative electrode materials with suitable operating voltages, excellent cycle performance and high energy density.
The specific capacity of the cobalt-based composite material (oxide, sulfide, phosphide and alloy) is up to 700-1000 mAh/g, which is 2-3 times of that of a graphite negative electrode, and the cobalt-based composite material has the advantages of wide availability, good stability and environmental friendliness, but the cobalt-based alloy has lower electron mobility and poor charge and discharge performance when used as a battery made of the negative electrode material.
How to improve the charge and discharge performance of such materials is one of the hot spots currently studied in the art. In patent CN112652699A, a LaF with P/N type transition is disclosed 3 Doped CoSb 3 Method for producing thermoelectric material by introducing LaF 3 The thermoelectric performance is optimized and the semiconductor type of the thermoelectric material can be influenced according to the doping amount thereof.
In patent CN113735181a, an antimony cobalt sulfide-carbon composite nanorod, and a preparation method and application thereof are disclosed, which adopt a method of solvothermal synthesis combined with high-temperature calcination to prepare a multi-level layered structure electrode material composed of the antimony cobalt sulfide nanorod, and obtain uniform carbon-coated antimony cobalt sulfide. The patent effectively improves the cycle performance and the multiplying power performance of the electrode material.
Disclosure of Invention
The invention mainly aims to provide a cobalt-based composite material, a preparation method and application thereof, and aims to solve the problems that in the prior art, the cobalt-based alloy has low electron mobility and is not suitable for being applied to a lithium ion battery cathode.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a cobalt-based composite material, comprising the steps of:
s1, coSb 3 Performing spark plasma sintering treatment on the mixed powder of graphitized carbon, and performing ball milling treatment to obtain an alloy precursor material;
s2, taking the alloy precursor material as a matrix, and depositing a non-metal semiconductor material layer on the matrix by utilizing an atomic vapor deposition method to obtain the cobalt-based composite material.
Further, the temperature of the spark plasma sintering treatment is 300-500 ℃ and the time is 5-10 min; preferably, the spark plasma sintering treatment is performed in an atmosphere of 50 to 80 MPa.
Further, in step S2, the atomic vapor deposition method includes:
taking a nonmetallic semiconductor material as a target material, and depositing for 1-3 s; secondly, purging for 50-70 s by inert gas; then, introducing an oxygen source for 4-8 s; secondly, purging with inert gas for 4-8 s; then water is introduced for 0.03 to 0.07s; finally, purging for 40-80 s by inert gas;
the steps are circulated for 10 to 100 times.
Further, coSb 3 The volume ratio of the catalyst to graphitized carbon is (1-5) (99-95).
Further, the grain size of the alloy precursor material is 0.2-1.7 mu m, and the deposition weight of the nonmetallic semiconductor material layer is 1-5 g.
Further, the nonmetallic semiconductor is granular, and the grain diameter is 100-200 nm; preferably, the non-metal semiconductor comprises one or more of silicon nanoparticles, boron nanoparticles, selenium nanoparticles.
Further, before step S1, the preparation method further includes: coSb is carried out 3 Performing ball milling treatment on the mixture and graphitized carbon to obtain CoSb 3 Mixed powder with graphitized carbon; the particle size after the preliminary ball milling treatment is preferably 0.2 to 1.5. Mu.m.
Further, graphitized carbon is one or more of carbon fiber, graphene and natural graphite.
In order to achieve the above object, according to one aspect of the present invention, there is provided a cobalt-based composite material prepared by the above preparation method
According to another aspect of the invention, there is provided the use of the cobalt-based composite material described above in a negative electrode material for a lithium battery.
By applying the technical scheme of the invention, graphitized carbon is doped into CoSb 3 And the nonmetallic semiconductor layer is wrapped to form a cobalt-based composite material. On the one hand, coSb 3 Containing octahedral voids which can accommodate the filling atoms, the invention forms p-type doping to them by carbon atoms, generally increasing their fermi energy, resulting in CoSb 3 The carbon-containing defects in the crystal lattice further improve the electron mobility of the crystal lattice, and the crystal lattice has good conductivity, fast charge performance and cycle performance. On the other hand, the invention further forms a nonmetallic coating with high capacity and large specific surface area on the outer layer of the alloy precursor material, which can effectively prevent cracking and oxidization of internal particles. In particular, the invention adopts the spark plasma sintering technology to form the alloy precursor material in advance, and then utilizes the atomic vapor deposition method to deposit the nonmetallic coating layer, thereby further improving the structural stability of the composite material and being beneficial to improving the cycle stability of the composite material. Based on the above reasons, the cobalt-based composite material obtained by the preparation method is very suitable to be used as a lithium ion battery anode material, and can effectively improve the battery capacity and improve the battery cycle performance.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
fig. 1 shows SEM morphology of a cobalt-based composite material prepared according to example 1 of the present invention.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
In order to solve the above-mentioned problems in the prior art, according to an aspect of the present invention, there is provided a method for preparing a cobalt-based composite material, comprising the steps of:
s1, coSb 3 Performing spark plasma sintering treatment on the mixed powder of graphitized carbon, and performing ball milling treatment to obtain an alloy precursor material;
s2, taking the alloy precursor material as a matrix, and depositing a non-metal semiconductor material layer on the matrix by utilizing an atomic vapor deposition method to obtain the cobalt-based composite material.
By applying the technical scheme of the invention, graphitized carbon is doped into CoSb 3 And the nonmetallic semiconductor layer is wrapped to form a cobalt-based composite material. On the one hand, coSb 3 Containing octahedral voids which can accommodate the filling atoms, the invention forms p-type doping to them by carbon atoms, generally increasing their fermi energy, resulting in CoSb 3 The carbon-containing defects in the crystal lattice further improve the electron mobility of the crystal lattice, and the crystal lattice has good conductivity, fast charge performance and cycle performance. On the other hand, the invention further forms a nonmetallic coating with high capacity and large specific surface area on the outer layer of the alloy precursor material, which can effectively prevent cracking and oxidization of internal particles. In particular, the invention adopts spark plasma sintering technology to form alloy precursor material in advance, and then utilizes atomic vapor deposition to deposit non-metal coating layer, thereby further improving the structural stability of the composite material and further ensuringIs beneficial to improving the circulation stability. Based on the above reasons, the cobalt-based composite material obtained by the preparation method is very suitable to be used as a lithium ion battery anode material, and can effectively improve the battery capacity and improve the battery cycle performance.
Specifically, in the C-Co substitution state, the s-orbital contribution of the carbon atom has a slight peak in HOMO, and thus there is a similar gain contribution to the fermi level between the s-and d-orbitals; the contribution of the d-orbitals to the fermi level is much greater than that of the s-orbitals; although again, the p orbitals are delocalized from Sb due to the broken symmetry, which contributes to some subtractive contribution. However, considering all the above cases, the fermi energy increases significantly as a whole.
On the other hand, in the preparation process, the non-metal semiconductor material layer is deposited by an atomic vapor deposition method, so that when the cobalt-based composite material obtained by the invention is used for a lithium ion battery anode material, dendrite production during intercalation and deintercalation of lithium ions in an alloy is effectively reduced, and the discharge specific capacity and the first charge-discharge efficiency of the material are further improved.
SEM morphology graph of the cobalt-based composite material prepared according to the invention is shown in figure 1. As can be seen from FIG. 1, the cobalt-based composite material of the present invention has a granular structure, uniform size distribution, and a particle size of 0.5-2 μm.
In a preferred embodiment, the spark plasma sintering treatment is carried out at a temperature of 300-500 ℃ for a time of 5-10 min; preferably, the spark plasma sintering treatment is performed in an atmosphere of 50 to 80 MPa. The spark plasma sintering treatment is carried out under the preferable condition, so that the graphitized carbon material and the alloy are more favorable to doping, and the C-Co substitution is carried out to improve the conductivity of the composite material.
In order to further improve the cycle performance, in a preferred embodiment, in step S2, the atomic vapor deposition method includes:
taking a nonmetallic semiconductor material as a target material, and depositing for 1-3 s; secondly, purging for 50-70 s by inert gas; then, introducing an oxygen source for 4-8 s; secondly, purging with inert gas for 4-8 s; then water is introduced for 0.03 to 0.07s; finally, purging for 40-80 s by inert gas;
the steps are circulated for 10 to 100 times.
The spark plasma sintering treatment is carried out according to the preferred process, which is more beneficial to improving the discharge capacity and the first charge-discharge efficiency.
In actual practice, the inert gases include, but are not limited to, nitrogen, argon, and the like.
To further enhance the conductivity, in a preferred embodiment, coSb 3 The volume ratio of the catalyst to graphitized carbon is (1-5) (99-95). Graphitized carbon to CoSb in the above volume ratio 3 Doping is carried out, so that the combination of graphitized carbon materials and alloys is facilitated, the total contribution of Fermi energy is improved, the conductivity of the composite material is improved, meanwhile, the occurrence of side reaction of lithium ions and negative electrode materials is reduced, the generation of lithium dendrites is reduced, and the cycle performance is improved.
In a preferred embodiment, the particle size of the alloy precursor material is 15 μm and the deposition weight of the layer of non-metallic semiconductor material is 1 to 5g. The conditions are preferable, so that the expansion and cracking of the alloy particles can be better prevented, and the structure of the cobalt-based composite material is stabilized.
In order to further improve the conductivity, in a preferred embodiment, the nonmetallic semiconductor is in the form of particles with a particle size of 100-200 nm; preferably, the non-metal semiconductor is one or more of silicon nanoparticles, boron nanoparticles, selenium nanoparticles. The common nonmetallic semiconductors can better realize the modification purpose of the invention. In practical applications, silicon nanoparticles have a relatively better effect than other non-metallic semiconductors.
In order to make the spark plasma sintering process more adequate, in a preferred embodiment, before step S1, the preparation method further comprises: coSb is carried out 3 Performing ball milling treatment on the mixture and graphitized carbon to obtain CoSb 3 Mixed powder with graphitized carbon; the particle size after the preliminary ball milling treatment is preferably 0.5 to 2. Mu.m.
In order to further enhance the effect of graphitized carbon doping modification, in a preferred embodiment, graphitized carbon is one or more of carbon fiber, graphene, natural graphite.
According to another aspect of the invention, a cobalt-based composite material prepared by the preparation method is provided. The material has excellent conductive property, conductivity, first discharge capacity, first efficiency, quick charge performance and cycle performance.
According to another aspect of the invention, there is provided the use of the cobalt-based composite material described above in a lithium battery. The lithium ion battery has the characteristics of conductivity, first discharge capacity, first efficiency, quick charge performance and cycle performance.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
S1-99.65 g CoSb 3 Adding 0.35g of Carbon Fiber (CF) into a ball mill, ball milling at 500 rpm for 1 hour, transferring the obtained composite powder into a carbon mold, discharging plasma sintering (SPS) at 300 ℃ for 10 minutes under the vacuum of 50Mpa, and ball milling in the ball mill to obtain CoSb 3 -CF (1.5 vol%) precursor material;
s2: transferring an alloy precursor material into a vacuum cavity by adopting an atomic vapor deposition method and taking the alloy precursor material as a matrix, and taking silicon nanoparticles as a target material, wherein the silicon nanoparticles are deposited on the alloy matrix according to the following parameters ((1) silicon nanoparticle material deposition for 1 second, (2) nitrogen purging for 60 seconds, (3) oxygen source introduction for 5 seconds, (4) nitrogen purging for 5 seconds, (5) water introduction for 0.05 seconds, (6) nitrogen purging for 50 seconds, and (7) 45 circles of circulation from the step (1) to obtain the silicon nanoparticle coated alloy composite material. The coating weight was 3g.
Example 2
S1-99.3 g CoSb 3 Adding 0.7g of graphene into a ball mill, ball milling at 600 rpm for 1 hour, transferring the obtained composite powder into a carbon mold, performing Spark Plasma Sintering (SPS) at 400 ℃ for 10 minutes under the vacuum of 50Mpa, and then placing into the ball mill for ball milling to obtain CoSb 3 -graphene (3 vol%) precursor material;
s2: transferring an alloy precursor material into a vacuum cavity by adopting an atomic vapor deposition method and taking the alloy precursor material as a matrix, and taking boron nano particles as a target material, wherein the silicon nano particles are deposited on the alloy matrix according to the following parameters ((1) boron nano particles are deposited for 1 second, (2) nitrogen is purged for 50 seconds, (3) oxygen is introduced for 4 seconds, (4) nitrogen is purged for 4 seconds, (5) water is introduced for 0.03 seconds, (6) nitrogen is purged for 40 seconds, and (7) 70 circles of circulation are started from the step (1), so that the boron nano particle coated alloy composite material is obtained. The coating weight was 4g.
Example 3
S1 99.7g CoSb 3 Adding 0.3g of natural graphite into a ball mill, ball milling at 400 rpm for 1 hour, transferring the composite powder obtained by mixing and ball milling into a carbon mold, performing Spark Plasma Sintering (SPS) at 300 ℃ for 15 minutes under the vacuum of 50Mpa, and then placing into the ball mill for ball milling to obtain CoSb 3 -natural graphite (1.2 vol%) precursor material;
s2: transferring an alloy precursor material into a vacuum cavity by adopting an atomic vapor deposition method, taking the alloy precursor material as a matrix, taking selenium nanoparticles as a target material, and depositing the selenium nanoparticles on the alloy matrix according to the following parameters ((1) depositing the selenium nanoparticle material for 3 seconds, (2) purging with nitrogen for 70 seconds, (3) purging with oxygen source for 8 seconds, (4) purging with nitrogen for 8 seconds, (5) purging with water for 0.07 seconds, (6) purging with nitrogen for 80 seconds, and (7) circulating 45 circles from the step (1) to obtain the selenium nanoparticle coated alloy composite material. The coating weight was 4g.
Example 4
S1 99.8g CoSb 3 Adding 0.2g of carbon fiber into a ball mill, ball milling at 500 rpm for 1 hour, transferring the composite powder obtained by mixing and ball milling into a carbon mold, performing Spark Plasma Sintering (SPS) at 300 ℃ for 10 minutes under the vacuum of 50Mpa, and then placing into the ball mill for ball milling to obtain CoSb 3 -CF (0.9 vol%) precursor material;
s2, preparing CoSb 3 CF (0.9 vol%) precursor material vapor deposition of silicon nanoparticle coated alloy composite was performed as per step S2 of example 1. The coating weight was 3g.
Example 5
S1 to 98.7g CoSb 3 Adding 1.3g of carbon fiber into a ball mill, ball milling for 1 hour at 500 revolutions/min, and mixingTransferring the composite powder obtained by ball milling into a carbon mold, performing Spark Plasma Sintering (SPS) at 300 ℃ for 10min under the vacuum of 50Mpa, and then placing into a ball mill for ball milling to obtain CoSb 3 -CF (5.6 vol%) precursor material;
s2, preparing CoSb 3 CF (5.6 vol%) precursor material vapor deposition of silicon nanoparticle coated alloy composite was performed as per step S2 of example 1. The coating weight was 3g.
Example 6
The difference from example 1 is that CoSb 3 The addition amounts of the catalyst and the carbon fiber are respectively 99.75g and 0.25g CoSb 3 -CF(1.0vol％)。
Example 7
The difference from example 1 is that CoSb 3 The addition amounts of the carbon fiber and the CoSb are 98.8g and 1.2g respectively 3 -CF(5.0vol％)。
Example 8
The difference from example 1 is that the spark plasma sintering temperature is 500℃and the vacuum 80MPa, sintering time is 5min.
Example 9
The difference from example 1 is that the coating mass of the silicon nanoparticles is 5g.
Example 10
The difference from example 1 is that the coating mass of the silicon nanoparticles is 1g.
Example 11
The difference from example 1 is that the coating mass of the silicon nanoparticles is 6g.
Comparative example 1
S1: coSb is carried out 3 Adding into a ball mill, ball milling for 1 hour at 500 rpm, and adding 99.65g CoSb 3 Transferring the silicon nano particles into a vacuum cavity and taking the silicon nano particles as a matrix, and depositing the silicon nano particles on the alloy matrix according to the following parameters ((1) silicon nano particle material for 1 second, (2) nitrogen purging for 60 seconds, (3) oxygen source introduction for 5 seconds, (4) nitrogen purging for 5 seconds, (5) water introduction for 0.05 seconds, (6) nitrogen purging for 50 seconds and (7) 45 circles of circulation from the step (1) to obtain the silicon nano particle coated alloy material. The coating mass of the silicon nanoparticles was 3g.
Comparative example 2
99.65g CoSb 3 The composite material was prepared according to step 2 in example 1 without spark plasma sintering by adding 0.35g of carbon fiber to a ball mill, ball milling at 500 rpm for 1 hour, and mixing the ball milled composite powder as a precursor.
Comparative example 3
Directly subjecting CoSb prepared in S1 of example 1 3 -CF (1.5 vol%) precursor material as negative electrode material.
The testing method comprises the following steps:
1. SEM test: the alloy composite material prepared in example 1 was subjected to SEM test, and the test results are shown in fig. 1.
2. Powder physical and chemical properties test: the negative electrode materials prepared in examples 1 to 11 and comparative examples 1 to 3 were subjected to tap density, specific surface area and specific capacity tests according to GB/T24533-2019 lithium ion battery graphite negative electrode material, and the results are shown in Table 1.
3. Electrochemical performance test: the negative electrode materials prepared in examples 1 to 11 and comparative examples 1 to 3 were assembled into button cells. The assembly method comprises the following steps: and adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and pulping, coating the mixture on a copper foil, and drying and rolling the mixture to obtain the negative electrode plate. The button cell was assembled in a glove box charged with hydrogen, and the electrochemical performance test was performed on a wuhan blue CT2001A type cell tester with a charge-discharge voltage ranging from 0.005V to 2.0V and a charge-discharge rate of 0.1C. The test results are shown in Table 2.
4. Soft package battery test: the negative electrode materials prepared in examples 1 to 11 and comparative examples 1 to 3 were prepared as negative electrode sheets, and were prepared as ternary materials (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) As positive electrode, with LiPF 6 Solution (EC+DEC solvent, volume ratio 1:1, liPF) 6 Concentration of 1.3 mol/L) was used as an electrolyte and cellgard 2400 was used as a separator to prepare a 5Ah pouch cell. And then testing the cycle performance and the multiplying power performance of the soft package battery.
Cycle performance test conditions: the charge and discharge current is 1C/1C, the voltage range is 2.8-4.2V, and the cycle number is 500.
Rate performance test conditions: charging rate: 1C/3C/5C/8C, discharge multiplying power 1C; voltage range: 2.8-4.2V.
The test results are shown in tables 3 and 4.
TABLE 1
| Project | Conductivity (S/cm) | Tap density (g/cm) 3 ) | Specific surface area (m) 2 /g) |
| Example 1 | 24.37 | 2.88 | 2.03 |
| Example 2 | 24.25 | 2.83 | 1.96 |
| Example 3 | 24.11 | 2.78 | 1.93 |
| Example 4 | 21.85 | 2.75 | 1.87 |
| Example 5 | 21.31 | 2.76 | 1.83 |
| Example 6 | 24.23 | 2.85 | 2.00 |
| Example 7 | 24.30 | 2.81 | 1.99 |
| Example 8 | 23.97 | 2.85 | 2.02 |
| Example 9 | 24.25 | 2.86 | 2.05 |
| Example 10 | 24.30 | 2.87 | 2.07 |
| Example 11 | 24.52 | 2.87 | 2.13 |
| Comparative example 1 | 19.56 | 2.74 | 1.86 |
| Comparative example 2 | 22.57 | 2.80 | 2.10 |
| Comparative example 3 | 21.72 | 2.73 | 1.36 |
TABLE 2
Table 2 continuation
TABLE 3 Table 3
TABLE 4 Table 4
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
as can be seen from Table 1, the conductivities of the composite materials prepared in the examples of the present invention are comparable to or higher than those of the comparative examples, and particularly the conductivities of examples 1 to 11 are mostly maintained at 24S/cm or more.
As can be seen from Table 2, the first discharge capacity of the lithium ion battery prepared by the invention can basically reach more than 400mAh/g, and the first charge and discharge efficiency is more than 90%.
As can be seen from Table 3, the cycling performance of the soft-packed battery prepared from the alloy material of the invention is superior to that of the comparative example, because the nonmetallic semiconductor wrapped by the outer layer can prevent the alloy particles from expanding and cracking in the aspect of 1C/1C multiplying power cycling performance, and the composite material structure is stabilized; meanwhile, the addition of the graphitized carbon material can also improve the conductivity of the graphitized carbon material and reduce the occurrence of side reactions, thereby improving the cycle performance.
As can be seen from Table 4, the soft pack batteries prepared in examples 1 to 11 of the present invention have a better constant current ratio and excellent cycle performance.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a cobalt-based composite material, the method comprising the steps of:
s1, coSb 3 Performing spark plasma sintering treatment on the mixed powder of graphitized carbon, and performing ball milling treatment to obtain an alloy precursor material;
s2, taking the alloy precursor material as a matrix, and depositing a non-metal semiconductor material layer on the matrix by utilizing an atomic vapor deposition method to obtain the cobalt-based composite material.
2. The preparation method according to claim 1, wherein the temperature of the spark plasma sintering treatment is 300-500 ℃ for 5-10 min; preferably, the spark plasma sintering treatment is performed under an atmosphere of 50 to 80 MPa.
3. The method according to claim 1 or 2, wherein in the step S2, the atomic vapor deposition method comprises:
taking a nonmetallic semiconductor material as a target material, and depositing for 1-3 s; secondly, purging for 50-70 s by inert gas; then, introducing an oxygen source for 4-8 s; secondly, purging with inert gas for 4-8 s; then water is introduced for 0.03 to 0.07s; finally, purging for 40-80 s by inert gas;
the steps are circulated for 10 to 100 times.
4. A production method according to any one of claims 1 to 3, characterized in that the CoSb 3 The volume ratio of the graphitized carbon to the graphitized carbon is (1-5) (99-95).
5. The method according to any one of claims 1 to 4, wherein the particle size of the alloy precursor material is 0.2 to 1.7 μm and the deposition weight of the nonmetallic semiconductor material layer is 1 to 5g.
6. The method according to any one of claims 1 to 5, wherein the nonmetallic semiconductor is in the form of particles having a particle diameter of 100 to 200nm; preferably, the non-metal semiconductor comprises one or more of silicon nanoparticles, boron nanoparticles, selenium nanoparticles.
7. The preparation method according to any one of claims 1 to 6, characterized in that before the step S1, the preparation method further comprises: subjecting the CoSb to 3 Performing ball milling treatment on the graphitized carbon to obtain the CoSb 3 And graphitizingA mixed powder of carbon; the particle size after the preliminary ball milling treatment is preferably 0.2 to 1.5. Mu.m.
8. The method according to any one of claims 1 to 7, wherein the graphitized carbon is one or more of carbon fiber, graphene, natural graphite.
9. A cobalt-based composite material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the cobalt-based composite material according to claim 9 in a negative electrode material for a lithium battery.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1614054A (en) * | 2004-06-25 | 2005-05-11 | 中国科学院上海硅酸盐研究所 | Cobalt antimonide based thermoelectric composite material and its preparation |
| CN102931335A (en) * | 2012-10-24 | 2013-02-13 | 东华大学 | Graphene compounded with stibine cobalt base skutterudite thermoelectric material and preparation method of material |
| CN114497507A (en) * | 2022-01-29 | 2022-05-13 | 辽宁中宏能源新材料股份有限公司 | Quick-filling graphite composite material and preparation method thereof |
| CN115207304A (en) * | 2022-05-17 | 2022-10-18 | 蜂巢能源科技股份有限公司 | Graphite cathode composite material, preparation method thereof and lithium ion battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1614054A (en) * | 2004-06-25 | 2005-05-11 | 中国科学院上海硅酸盐研究所 | Cobalt antimonide based thermoelectric composite material and its preparation |
| CN102931335A (en) * | 2012-10-24 | 2013-02-13 | 东华大学 | Graphene compounded with stibine cobalt base skutterudite thermoelectric material and preparation method of material |
| CN114497507A (en) * | 2022-01-29 | 2022-05-13 | 辽宁中宏能源新材料股份有限公司 | Quick-filling graphite composite material and preparation method thereof |
| CN115207304A (en) * | 2022-05-17 | 2022-10-18 | 蜂巢能源科技股份有限公司 | Graphite cathode composite material, preparation method thereof and lithium ion battery |
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