CN112242513A - Tube-wire structure silicon-carbon negative electrode material and preparation method thereof - Google Patents
Tube-wire structure silicon-carbon negative electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN112242513A CN112242513A CN202011120103.3A CN202011120103A CN112242513A CN 112242513 A CN112242513 A CN 112242513A CN 202011120103 A CN202011120103 A CN 202011120103A CN 112242513 A CN112242513 A CN 112242513A
- Authority
- CN
- China
- Prior art keywords
- spinning solution
- silicon
- tube
- layer spinning
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 title claims description 19
- 238000009987 spinning Methods 0.000 claims abstract description 168
- 239000010410 layer Substances 0.000 claims abstract description 121
- 239000012792 core layer Substances 0.000 claims abstract description 60
- 239000000835 fiber Substances 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 24
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 238000005507 spraying Methods 0.000 claims abstract description 13
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 174
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 116
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 65
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000011863 silicon-based powder Substances 0.000 claims description 27
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000787 lecithin Substances 0.000 claims description 18
- 229940067606 lecithin Drugs 0.000 claims description 18
- 235000010445 lecithin Nutrition 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 229940057995 liquid paraffin Drugs 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 13
- 230000009471 action Effects 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 230000005611 electricity Effects 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- 230000003068 static effect Effects 0.000 claims description 12
- 239000012300 argon atmosphere Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 11
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 229910052710 silicon Inorganic materials 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010703 silicon Substances 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000002121 nanofiber Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 26
- 238000005516 engineering process Methods 0.000 description 18
- 238000001816 cooling Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002210 silicon-based material Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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 preparation method of a tubular-linear structure silicon-carbon anode material, which comprises the steps of preparing a shell layer spinning solution, a core layer spinning solution and a middle layer spinning solution; adding a shell layer spinning solution into the outer tube, a middle layer spinning solution into the middle tube and a core layer spinning solution into the inner tube by adopting a three-layer coaxial spinning nozzle consisting of three tubes, namely an outer tube, a middle tube and an inner tube, and preparing the composite coaxial fiber by a transverse spraying type electrostatic spinning method; and pre-oxidizing the composite coaxial fibers, and then carbonizing to obtain the tube-line structure silicon-carbon cathode material. The prepared nano-fiber cathode material with the pipe-line structure simultaneously has fiber and hollow structures, the volume expansion of silicon is limited by carbon in the C and Si blended material of the core layer, the full carbon shell of the outermost layer provides protection, and the cavity between the core layer and the shell layer provides a buffer space for the volume expansion of the silicon, so that the volume expansion problem of the silicon is minimized in the charging and discharging process, and the cycle performance of the battery is improved.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a tube-wire structure silicon-carbon negative electrode material and a preparation method thereof.
Background
The lithium battery has excellent performance, is widely applied, and plays an increasingly important role in the fields of movable electronic equipment, such as smart phones, notebook computers, new energy automobiles, household small-sized appliances, medical cardiac pacemakers and the like. With the research and development of lithium ion secondary batteries, the performance and capacity of lithium batteries are increasingly important. However, the commercial lithium battery cannot meet the demand of people due to the low theoretical capacity. Therefore, the research and development of the lithium ion battery with high capacity and high performance and the electrode material thereof have important significance.
Silicon is a lithium ion battery cathode material with great development prospect, during charging, the silicon can form an alloy with lithium to store lithium ions, energy storage and release are realized through the insertion and extraction of the lithium ions, each silicon atom can contain 4.4 lithium atoms at most, and Li with the theoretical capacity of 4200 m-Ah/g is formed22Si5The alloy is an order of magnitude higher than graphite (372 m. Ah/g) negative electrodes used in commercial lithium batteries. However, during the use of the silicon-based material in the lithium ion battery, the volume of the silicon-based material can expand, which causes mechanical failure and affects the service life of the lithium battery. In addition, as for silicon materials, the conductivity of the silicon materials is poor, and the charge and discharge performance of the lithium battery is affected. Therefore, the key to the research on the silicon-based materials is to suppress the volume expansion thereof and to improve the electrical conductivity thereof. The traditional method for solving the problem is to prepare a carbon-coated silicon material, and use the skeleton structure of carbon as a buffer carrier of volume change in the charging and discharging processes of the carbon, so as to reduce the reduction of the battery performance caused by the volume change. But do notBecause the volume change of the material is very large in the charging and discharging processes, the simple carbon coating structure is not enough to completely overcome the problem of volume expansion.
Patent 201610993141.7 discloses a SnO2The preparation method of the @ C lithium ion battery cathode material adopts double-layer coaxial spinning, a simple carbon-coated structure is obtained, the core layer has no extra constraint force, and the problem of Si volume expansion is not fully solved. The document with the application number of 201810224334.5 discloses a method for preparing a carbon-coated silicon lithium ion battery cathode material, hydrofluoric acid is needed in the preparation process, the danger coefficient is high, and the strength of the material is correspondingly reduced after the material is etched by the hydrofluoric acid.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the technical problem of providing a tube-wire structure silicon-carbon anode material and a preparation method thereof.
The technical scheme for solving the technical problem is to provide a preparation method of a tube-wire type structure silicon-carbon anode material, which is characterized by comprising the following steps:
(1) preparing a shell layer spinning solution, a core layer spinning solution and an intermediate layer spinning solution;
the shell spinning solution is a uniform PAN solution; the core layer spinning solution is prepared by adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion solution; the middle layer spinning solution is an emulsion or a solution which is immiscible with the shell layer spinning solution and the core layer spinning solution and can be removed in a subsequent pre-oxidation process;
(2) preparing composite coaxial fibers: adding the shell layer spinning solution prepared in the step (1) into the outer tube, adding the middle layer spinning solution into the middle tube, adding the core layer spinning solution into the inner tube by adopting a three-layer coaxial spinning nozzle consisting of three tubes, namely an outer tube, a middle tube and an inner tube, and preparing the composite coaxial fiber of [ PAN + silicon powder ] @ [ middle layer ] @ PAN by a transverse spraying type electrostatic spinning method under the action of high-voltage static electricity;
(3) preparing a silicon-carbon anode material with a pipe-line structure: pre-oxidizing the composite coaxial fiber obtained in the step (2) to ensure cross-linking of PAN and complete elimination of the intermediate layer; and then carbonizing to obtain the silicon-carbon cathode material with the pipe-line structure.
Compared with the prior art, the invention has the beneficial effects that:
(1) the prepared pipe-line structure [ C + Si ] @ C nanofiber negative electrode material has a fiber and hollow structure, carbon in the C and Si blended material of the core layer limits the volume expansion of silicon, the outermost full carbon shell can continuously provide a layer of protection, and most importantly, a buffer space is further provided for the volume expansion of the silicon by the cavity between the core layer and the shell layer, so that the volume expansion problem of the silicon is minimized in the whole charging and discharging process, and the cycle performance of a battery is greatly improved.
(2) The shell layer C and the core layer C provide a double-carbon-layer conductive mechanism, so that the conductivity of the material is improved, the pulverization of the material can be reduced, and the problem of poor conductivity of the existing core-shell structure is solved.
(3) The invention adopts three-layer coaxial electrostatic spinning to prepare the composite coaxial fiber in one step, the spinning solution of the middle layer needs to be immiscible with the spinning solutions of the shell layer and the core layer, but the requirements on the inner layer solution and the outer layer solution are not met (miscible or insoluble). Compared with the current common method that the inner layer and the outer layer of the coaxial cable are not mixed, the invention enlarges the usable range of key materials. Meanwhile, compared with the traditional coating method, the method is simple and convenient, strong acid etching is not needed, and the safety and the environmental protection are greatly improved.
(4) The invention realizes the crosslinking of PAN and the total elimination of the intermediate layer by controlling the pre-oxidation process.
(5) The battery assembled by the cathode material has good cycle performance and higher coulombic efficiency.
Drawings
FIG. 1 is a TEM photograph of a composite coaxial fiber prepared in example 9 of the present invention.
Fig. 2 is a TEM photograph of the silicon carbon anode material prepared in example 9 of the present invention.
FIG. 3 is a graph of specific capacity versus coulombic efficiency for example 9 of the present invention.
Detailed Description
Specific examples of the present invention are given below. The specific examples are only intended to illustrate the invention in further detail and do not limit the scope of protection of the claims of the present application.
The invention provides a preparation method (method for short) of a silicon-carbon anode material with a pipeline-type structure, which is characterized by comprising the following steps:
(1) preparing a shell layer spinning solution, a core layer spinning solution and an intermediate layer spinning solution;
the shell layer spinning solution is a uniform PAN solution, wherein the mass of PAN accounts for 8-15% of that of the shell layer spinning solution;
the core layer spinning solution is a uniform dispersion liquid formed by adding silicon powder into a PAN solution, wherein the mass of the silicon powder accounts for 5-10% of that of the core layer spinning solution, and the mass of the PAN accounts for 4-8% of that of the core layer spinning solution;
in the PAN solution, the solvent is a good PAN solvent which ensures that PAN can be formed into fibers in the electrostatic spinning process, and specifically, the PAN is added into DMF or ethylene carbonate and stirred for more than 3 hours to form a uniform DMF or ethylene carbonate solution of PAN.
The middle layer spinning solution is an emulsion or a solution which is immiscible with the shell layer spinning solution and the core layer spinning solution and can be removed in a subsequent pre-oxidation process, and specifically is an emulsion formed by adding lecithin and deionized water into liquid paraffin, wherein the mass of the lecithin accounts for 5-12% of that of the middle layer spinning solution, and the mass of the deionized water accounts for 2-5% of that of the middle layer spinning solution; or, adding PMMA or PVA into the mixed solution of acetone and DMF to form a solution, wherein the mass of PMMA or PVA accounts for 8-15% of the mass of the middle layer spinning solution, and the mass of acetone accounts for 20-40% of the mass of the middle layer spinning solution;
(2) preparing composite coaxial fibers: adding the shell layer spinning solution prepared in the step (1) into an outer pipe with the inner diameter of 1.64-1.94mm by adopting a three-layer coaxial spinning nozzle consisting of three stainless steel thin pipes with different inner diameters, an intermediate pipe and an inner pipe, adding the intermediate layer spinning solution into the intermediate pipe with the inner diameter of 0.92-1.11mm, adding the core layer spinning solution into the inner pipe with the inner diameter of 0.3-0.42mm, and preparing the composite coaxial fiber of [ PAN + silicon powder ] @ [ intermediate layer ] @ PAN by a transverse spraying type electrostatic spinning method under the action of high-voltage static electricity;
the spinning head and the receiving plate are vertically placed, namely the receiving plate is vertical to the horizontal plane, the applied voltage is 15-20 KV, the receiving distance is 15-20 cm, the temperature is 25 ℃ at room temperature, the relative humidity is 40% -50%, and the advancing speeds of the shell layer spinning solution, the middle layer spinning solution and the core layer spinning solution are 3-6 ml/h, 1-3 ml/h and 0.1-1 ml/h respectively;
@ is expressed in that [ PAN + silicon powder ] is wrapped in the [ intermediate layer ], and the [ intermediate layer ] is wrapped in the PAN;
(3) preparing a silicon-carbon anode material with a pipe-line structure: carrying out heat treatment on the composite coaxial fiber obtained in the step (2), pre-oxidizing the composite coaxial fiber at 260-290 ℃ for 1-3 h in the air atmosphere at the heating rate of 1-5 ℃/min, and ensuring the crosslinking of the PAN of the shell layer and the total elimination of the middle layer in the pre-oxidation stage; then transferring the material to a tubular furnace, carbonizing the material for 1-2 hours at 600-900 ℃ in an argon atmosphere, wherein the heating rate is 2-5 ℃/min, and providing high conductivity for the material in a carbonization stage; and finally, cooling at the speed of 2-10 ℃/min to obtain the silicon-carbon cathode material with the pipe-line structure.
The invention also provides the tube-line structure silicon-carbon cathode material prepared by the preparation method of the tube-line structure silicon-carbon cathode material.
Example 1
(1) Adding PAN into DMF, stirring for 6h at 80 ℃ to form a light yellow solution, namely a shell spinning solution, wherein the mass fractions of the substances are respectively as follows: PAN 15% and DMF 85%;
adding lecithin and deionized water into liquid paraffin to form emulsion, namely the interlayer spinning solution, wherein the mass fractions of the substances are respectively as follows: 12% of lecithin, 5% of deionized water and 83% of liquid paraffin;
adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion liquid, namely a core layer spinning solution, wherein the mass fractions of the substances are as follows: 5% of silicon powder, 5% of PAN and 90% of DMF;
(2) spinning by adopting a coaxial electrostatic spinning technology; the spinning head adopts a three-layer coaxial spinning head consisting of three stainless steel thin tubes with different specifications, and the inner diameters of the inner tube, the middle tube and the outer tube are respectively 0.3-0.42mm, 0.92-1.11mm and 1.64-1.94 mm; adding the shell layer spinning solution obtained in the step (1) into an outer pipe, adding the middle layer spinning solution into a middle pipe, and adding the core layer spinning solution into an inner pipe; adopting an electrostatic spinning technology and a transverse spraying mode, wherein a nozzle is vertical to a receiving plate, the applied voltage is 20KV, the receiving distance is 20cm, the temperature is 25 ℃ at room temperature, the relative humidity is 40% -50%, and the advancing speeds of a shell layer spinning solution, an intermediate layer spinning solution and a core layer spinning solution are respectively 6ml/h, 3ml/h and 1 ml/h; under the action of high-voltage static electricity, composite coaxial fibers are prepared;
(3) and (2) carrying out heat treatment on the prepared composite coaxial fiber, firstly carrying out pre-oxidation for 2h in an air atmosphere at 280 ℃, wherein the heating rate is 2 ℃/min, then transferring the composite coaxial fiber into a tube furnace for carbonization for 1h at 800 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, and carrying out cooling treatment to obtain the [ C + Si ] @ C negative electrode material with a tube-line structure.
Tests show that the coulombic efficiency is about 99.3 percent on average, and the specific capacity retention rate is 90 percent after 100 times of circulation.
Example 2
(1) Adding PAN into DMF, stirring for 6h at 80 ℃ to form a light yellow solution, namely a shell spinning solution, wherein the mass fractions of the substances are respectively as follows: PAN 15% and DMF 85%;
adding lecithin and deionized water into liquid paraffin to form emulsion, namely the interlayer spinning solution, wherein the mass fractions of the substances are respectively as follows: 12% of lecithin, 5% of deionized water and 83% of liquid paraffin;
adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion liquid, namely a core layer spinning solution, wherein the mass fractions of the substances are as follows: 6% of silicon powder, 6% of PAN and 88% of DMF;
(2) spinning by adopting a coaxial electrostatic spinning technology; the spinning head adopts a three-layer coaxial spinning head consisting of three stainless steel thin tubes with different specifications, and the inner diameters of the inner tube, the middle tube and the outer tube are respectively 0.3-0.42mm, 0.92-1.11mm and 1.64-1.94 mm; adding the shell layer spinning solution obtained in the step (1) into an outer pipe, adding the middle layer spinning solution into a middle pipe, and adding the core layer spinning solution into an inner pipe; adopting an electrostatic spinning technology and a transverse spraying mode, wherein a nozzle is vertical to a receiving plate, the applied voltage is 20KV, the receiving distance is 20cm, the temperature is 25 ℃ at room temperature, the relative humidity is 40% -50%, and the advancing speeds of a shell layer spinning solution, an intermediate layer spinning solution and a core layer spinning solution are respectively 6ml/h, 3ml/h and 1 ml/h; under the action of high-voltage static electricity, composite coaxial fibers are prepared;
(3) and (2) carrying out heat treatment on the prepared composite coaxial fiber, firstly carrying out pre-oxidation for 2h in an air atmosphere at 280 ℃, wherein the heating rate is 2 ℃/min, then transferring the composite coaxial fiber into a tube furnace for carbonization for 1h at 800 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, and carrying out cooling treatment to obtain the [ C + Si ] @ C negative electrode material with a tube-line structure.
Tests show that the coulombic efficiency is about 99.2 percent on average, and the specific capacity retention rate is 89 percent after 100 times of circulation.
Example 3
(1) Adding PAN into DMF, stirring for 6h at 80 ℃ to form a light yellow solution, namely a shell spinning solution, wherein the mass fractions of the substances are respectively as follows: PAN 15% and DMF 85%;
adding lecithin and deionized water into liquid paraffin to form emulsion, namely the interlayer spinning solution, wherein the mass fractions of the substances are respectively as follows: 12% of lecithin, 5% of deionized water and 83% of liquid paraffin;
adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion liquid, namely a core layer spinning solution, wherein the mass fractions of the substances are as follows: 10% of silicon powder, 4% of PAN and 86% of DMF;
(2) spinning by adopting a coaxial electrostatic spinning technology; the spinning head adopts a three-layer coaxial spinning head consisting of three stainless steel thin tubes with different specifications, and the inner diameters of the inner tube, the middle tube and the outer tube are respectively 0.3-0.42mm, 0.92-1.11mm and 1.64-1.94 mm; adding the shell layer spinning solution obtained in the step (1) into an outer pipe, adding the middle layer spinning solution into a middle pipe, and adding the core layer spinning solution into an inner pipe; adopting an electrostatic spinning technology and a transverse spraying mode, wherein a nozzle is vertical to a receiving plate, the applied voltage is 20KV, the receiving distance is 20cm, the temperature is 25 ℃ at room temperature, the relative humidity is 40% -50%, and the advancing speeds of a shell layer spinning solution, an intermediate layer spinning solution and a core layer spinning solution are respectively 6ml/h, 3ml/h and 1 ml/h; under the action of high-voltage static electricity, composite coaxial fibers are prepared;
(3) and (2) carrying out heat treatment on the prepared composite coaxial fiber, firstly carrying out pre-oxidation for 2h in an air atmosphere at 280 ℃, wherein the heating rate is 2 ℃/min, then transferring the composite coaxial fiber into a tube furnace for carbonization for 1h at 800 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, and carrying out cooling treatment to obtain the [ C + Si ] @ C negative electrode material with a tube-line structure.
Tests show that the coulombic efficiency is about 99 percent on average, and the specific capacity retention rate is 86.3 percent after 100 times of circulation.
Example 4
(1) Adding PAN into DMF, stirring for 6h at 80 ℃ to form a light yellow solution, namely a shell spinning solution, wherein the mass fractions of the substances are respectively as follows: PAN 8% and DMF 92%;
adding PVA into acetone and DMF to form a solution, namely the middle layer spinning solution, wherein the mass fractions of the materials are respectively as follows: 10% of PVA, 40% of acetone and 50% of DMF;
adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion liquid, namely a core layer spinning solution, wherein the mass fractions of the substances are as follows: 5% of silicon powder, 5% of PAN and 90% of DMF;
(2) spinning by adopting a coaxial electrostatic spinning technology; the spinning head adopts a three-layer coaxial spinning head consisting of three stainless steel thin tubes with different specifications, and the inner diameters of the inner tube, the middle tube and the outer tube are respectively 0.3-0.42mm, 0.92-1.11mm and 1.64-1.94 mm; adding the shell layer spinning solution obtained in the step (1) into an outer pipe, adding the middle layer spinning solution into a middle pipe, and adding the core layer spinning solution into an inner pipe; adopting an electrostatic spinning technology and a transverse spraying mode, wherein a nozzle is vertical to a receiving plate, the applied voltage is 20KV, the receiving distance is 20cm, the temperature is 25 ℃ at room temperature, the relative humidity is 40% -50%, and the advancing speeds of the shell layer spinning solution, the middle layer spinning solution and the core layer spinning solution are 5ml/h, 2.5ml/h and 0.8ml/h respectively; under the action of high-voltage static electricity, composite coaxial fibers are prepared;
(3) and (2) carrying out heat treatment on the prepared composite coaxial fiber, firstly carrying out pre-oxidation for 2h in an air atmosphere at 280 ℃, wherein the heating rate is 2 ℃/min, then transferring the composite coaxial fiber into a tube furnace for carbonization for 1h at 800 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, and carrying out cooling treatment to obtain the [ C + Si ] @ C negative electrode material with a tube-line structure.
Tests show that the coulombic efficiency is about 99.4 percent on average, and the specific capacity retention rate is 84 percent after 100 times of circulation.
Example 5
(1) Adding PAN into DMF, stirring for 6h at 80 ℃ to form a light yellow solution, namely a shell spinning solution, wherein the mass fractions of the substances are respectively as follows: PAN 8% and DMF 92%;
adding lecithin and deionized water into liquid paraffin to form emulsion, namely the interlayer spinning solution, wherein the mass fractions of the substances are respectively as follows: 12% of lecithin, 5% of deionized water and 83% of liquid paraffin;
adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion liquid, namely a core layer spinning solution, wherein the mass fractions of the substances are as follows: 10% of silicon powder, 4% of PAN and 86% of DMF;
(2) spinning by adopting a coaxial electrostatic spinning technology; the spinning head adopts a three-layer coaxial spinning head consisting of three stainless steel thin tubes with different specifications, and the inner diameters of the inner tube, the middle tube and the outer tube are respectively 0.3-0.42mm, 0.92-1.11mm and 1.64-1.94 mm; adding the shell layer spinning solution obtained in the step (1) into an outer pipe, adding the middle layer spinning solution into a middle pipe, and adding the core layer spinning solution into an inner pipe; adopting an electrostatic spinning technology and a transverse spraying mode, wherein a nozzle is vertical to a receiving plate, the applied voltage is 20KV, the receiving distance is 20cm, the temperature is 25 ℃ at room temperature, the relative humidity is 40% -50%, and the advancing speeds of the shell layer spinning solution, the middle layer spinning solution and the core layer spinning solution are 5ml/h, 2.5ml/h and 0.8ml/h respectively; under the action of high-voltage static electricity, composite coaxial fibers are prepared;
(3) and (2) carrying out heat treatment on the prepared composite coaxial fiber, firstly carrying out pre-oxidation for 2h in an air atmosphere at 280 ℃, wherein the heating rate is 2 ℃/min, then transferring the composite coaxial fiber into a tube furnace for carbonization for 1h at 800 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, and carrying out cooling treatment to obtain the [ C + Si ] @ C negative electrode material with a tube-line structure.
Tests show that the coulombic efficiency is about 99.35 percent on average, and the specific capacity retention rate is 85 percent after 100 times of circulation.
Example 6
(1) Adding PAN into DMF, stirring for 6h at 80 ℃ to form a light yellow solution, namely a shell spinning solution, wherein the mass fractions of the substances are respectively as follows: PAN 8% and DMF 92%;
adding PMMA into acetone and DMF to form a solution, namely the middle layer spinning solution, wherein the mass fractions of the substances are respectively as follows: 10% of PMMA, 40% of acetone and 50% of DMF;
adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion liquid, namely a core layer spinning solution, wherein the mass fractions of the substances are as follows: 6% of silicon powder, 6% of PAN and 88% of DMF;
(2) spinning by adopting a coaxial electrostatic spinning technology; the spinneret is a three-layer coaxial spinneret consisting of three stainless steel thin tubes with different specifications, and the inner diameters of the inner tube, the middle tube and the outer tube are respectively 0.3-0.42mm, 0.92-1.11mm and 1.64-1.94 mm; adding the shell layer spinning solution obtained in the step (1) into an outer pipe, adding the middle layer spinning solution into a middle pipe, and adding the core layer spinning solution into an inner pipe; adopting an electrostatic spinning technology and a transverse spraying mode, wherein a nozzle is vertical to a receiving plate, the applied voltage is 20KV, the receiving distance is 20cm, the temperature is 25 ℃ at room temperature, the relative humidity is 40% -50%, and the advancing speeds of the shell layer spinning solution, the middle layer spinning solution and the core layer spinning solution are 5ml/h, 2.5ml/h and 0.8ml/h respectively; under the action of high-voltage static electricity, composite coaxial fibers are prepared;
(3) and (2) carrying out heat treatment on the prepared composite coaxial fiber, firstly carrying out pre-oxidation for 2h in an air atmosphere at 280 ℃, wherein the heating rate is 2 ℃/min, then transferring the composite coaxial fiber into a tube furnace for carbonization for 1h at 800 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, and carrying out cooling treatment to obtain the [ C + Si ] @ C negative electrode material with a tube-line structure.
Tests show that the coulombic efficiency is about 99.43% on average, and the specific capacity retention rate is 86% after 100 times of circulation.
Example 7
(1) Adding PAN into DMF, stirring for 6h at 80 ℃ to form a light yellow solution, namely a shell spinning solution, wherein the mass fractions of the substances are respectively as follows: PAN 12% and DMF 88%;
adding lecithin and deionized water into liquid paraffin to form emulsion, namely the interlayer spinning solution, wherein the mass fractions of the substances are respectively as follows: 10% of lecithin, 4% of deionized water and 86% of liquid paraffin;
adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion liquid, namely a core layer spinning solution, wherein the mass fractions of the substances are as follows: 6% of silicon powder, 6% of PAN and 88% of DMF;
(2) spinning by adopting a coaxial electrostatic spinning technology; the spinneret is a three-layer coaxial spinneret consisting of three stainless steel thin tubes with different specifications, and the inner diameters of the inner tube, the middle tube and the outer tube are respectively 0.3-0.42mm, 0.92-1.11mm and 1.64-1.94 mm; adding the shell layer spinning solution obtained in the step (1) into an outer pipe, adding the middle layer spinning solution into a middle pipe, and adding the core layer spinning solution into an inner pipe; adopting an electrostatic spinning technology and a transverse spraying mode, wherein a nozzle is vertical to a receiving plate, the applied voltage is 20KV, the receiving distance is 20cm, the temperature is 25 ℃ at room temperature, the relative humidity is 40% -50%, and the advancing speeds of a shell layer spinning solution, an intermediate layer spinning solution and a core layer spinning solution are 5ml/h, 2.5ml/h and 1ml/h respectively; under the action of high-voltage static electricity, composite coaxial fibers are prepared;
(3) and (2) carrying out heat treatment on the prepared composite coaxial fiber, firstly carrying out pre-oxidation for 2h in an air atmosphere at 280 ℃, wherein the heating rate is 2 ℃/min, then transferring the composite coaxial fiber into a tube furnace for carbonization for 1h at 800 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, and carrying out cooling treatment to obtain the [ C + Si ] @ C negative electrode material with a tube-line structure.
Tests show that the coulombic efficiency is about 99.52 percent on average, and the specific capacity retention rate is 88 percent after 100 times of circulation.
Comparative example 1
This comparative example is the same as example 7, the only difference being a carbonization temperature of 700 ℃.
Comparative example 2
This comparative example is identical to example 7, the only difference being that the pre-oxidation temperature is 270 ℃.
Example 8
(1) Adding PAN into DMF, stirring for 6h at 80 ℃ to form a light yellow solution, namely a shell spinning solution, wherein the mass fractions of the substances are respectively as follows: PAN 12% and DMF 88%;
adding lecithin and deionized water into liquid paraffin to form emulsion, namely the interlayer spinning solution, wherein the mass fractions of the substances are respectively as follows: 12% of lecithin, 5% of deionized water and 83% of liquid paraffin;
adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion liquid, namely a core layer spinning solution, wherein the mass fractions of the substances are as follows: 6% of silicon powder, 6% of PAN and 88% of DMF;
(2) spinning by adopting a coaxial electrostatic spinning technology; the spinneret is a three-layer coaxial spinneret consisting of three stainless steel thin tubes with different specifications, and the inner diameters of the inner tube, the middle tube and the outer tube are respectively 0.3-0.42mm, 0.92-1.11mm and 1.64-1.94 mm; adding the shell layer spinning solution obtained in the step (1) into an outer pipe, adding the middle layer spinning solution into a middle pipe, and adding the core layer spinning solution into an inner pipe; adopting an electrostatic spinning technology and a transverse spraying mode, wherein a nozzle is vertical to a receiving plate, the applied voltage is 20KV, the receiving distance is 20cm, the temperature is 25 ℃ at room temperature, the relative humidity is 40% -50%, and the advancing speeds of the shell layer spinning solution, the middle layer spinning solution and the core layer spinning solution are 5ml/h, 2.5ml/h and 0.8ml/h respectively; under the action of high-voltage static electricity, composite coaxial fibers are prepared;
(3) and (2) carrying out heat treatment on the prepared composite coaxial fiber, firstly carrying out pre-oxidation for 2h in an air atmosphere at 280 ℃, wherein the heating rate is 2 ℃/min, then transferring the composite coaxial fiber into a tube furnace for carbonization for 1h at 800 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, and carrying out cooling treatment to obtain the [ C + Si ] @ C negative electrode material with a tube-line structure.
Tests show that the coulombic efficiency is about 99.5 percent on average, and the specific capacity retention rate is 88 percent after 100 times of circulation.
Example 9
(1) Adding PAN into DMF, stirring for 6h at 80 ℃ to form a light yellow solution, namely a shell spinning solution, wherein the mass fractions of the substances are respectively as follows: PAN 12% and DMF 88%;
adding lecithin and deionized water into liquid paraffin to form emulsion, namely the interlayer spinning solution, wherein the mass fractions of the substances are respectively as follows: 9% of lecithin, 8% of deionized water and 83% of liquid paraffin;
adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion liquid, namely a core layer spinning solution, wherein the mass fractions of the substances are as follows: 6% of silicon powder, 6% of PAN and 88% of DMF;
(2) spinning by adopting a coaxial electrostatic spinning technology; the spinneret is a three-layer coaxial spinneret consisting of three stainless steel thin tubes with different specifications, and the inner diameters of the inner tube, the middle tube and the outer tube are respectively 0.3-0.42mm, 0.92-1.11mm and 1.64-1.94 mm; adding the shell layer spinning solution obtained in the step (1) into an outer pipe, adding the middle layer spinning solution into a middle pipe, and adding the core layer spinning solution into an inner pipe; adopting an electrostatic spinning technology and a transverse spraying mode, wherein a nozzle is vertical to a receiving plate, the applied voltage is 20KV, the receiving distance is 20cm, the temperature is 25 ℃ at room temperature, the relative humidity is 40% -50%, and the advancing speeds of the shell layer spinning solution, the middle layer spinning solution and the core layer spinning solution are 5ml/h, 2.5ml/h and 0.8ml/h respectively; under the action of high-voltage static electricity, composite coaxial fibers are prepared;
in fig. 1, the core layer, the intermediate layer and the shell layer are represented in the figure in the order of color from dark to light. The core layer and the intermediate layer as well as the intermediate layer and the shell layer have obvious different colors, which indicates that the composite coaxial fiber is successfully prepared.
(3) And (2) carrying out heat treatment on the prepared composite coaxial fiber, firstly carrying out pre-oxidation for 2h in an air atmosphere at 280 ℃, wherein the heating rate is 2 ℃/min, then transferring the composite coaxial fiber into a tube furnace for carbonization for 1h at 800 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃/min, and carrying out cooling treatment to obtain the [ C + Si ] @ C negative electrode material with a tube-line structure.
As can be seen from fig. 2, there are distinct dividing regions between the core layer and the shell layer, i.e., regions on both sides of the core layer in the figure that transmit bright light. The reason is that the material only leaves the core layer and the shell layer with the intermediate layer removed and the carbonization process, and a cavity structure is formed between the core layer and the shell layer.
As can be seen from fig. 3, the coulombic efficiency was found to be about 99.48% on average, and the specific capacity retention rate after 100 cycles was 87.5%.
The electrochemical performance test results of the silicon-carbon negative electrode materials prepared in the above examples and comparative examples when used in a lithium ion battery are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the coulombic efficiency after 100 cycles can reach more than 98% at most, and the cycle stability is greatly improved. The electrochemical performance of the lithium battery cathode material disclosed by the embodiment of the invention is obviously superior to that of a comparative example, which is the result of synergistic effect of all the composition structures in all the steps of the invention, the problem of expansibility of silicon is overcome, and the effect of the invention is proved.
Nothing in this specification is said to apply to the prior art.
Claims (10)
1. A preparation method of a tube-wire structure silicon-carbon negative electrode material is characterized by comprising the following steps:
(1) preparing a shell layer spinning solution, a core layer spinning solution and an intermediate layer spinning solution;
the shell spinning solution is a uniform PAN solution; the core layer spinning solution is prepared by adding silicon powder into a DMF (dimethyl formamide) solution of PAN (polyacrylonitrile) to form a dispersion solution; the middle layer spinning solution is an emulsion or a solution which is immiscible with the shell layer spinning solution and the core layer spinning solution and can be removed in a subsequent pre-oxidation process;
(2) preparing composite coaxial fibers: adding the shell layer spinning solution prepared in the step (1) into the outer tube, adding the middle layer spinning solution into the middle tube, adding the core layer spinning solution into the inner tube by adopting a three-layer coaxial spinning nozzle consisting of three tubes, namely an outer tube, a middle tube and an inner tube, and preparing the composite coaxial fiber of [ PAN + silicon powder ] @ [ middle layer ] @ PAN by a transverse spraying type electrostatic spinning method under the action of high-voltage static electricity;
(3) preparing a silicon-carbon anode material with a pipe-line structure: pre-oxidizing the composite coaxial fiber obtained in the step (2) to ensure cross-linking of PAN and complete elimination of the intermediate layer; and then carbonizing to obtain the silicon-carbon cathode material with the pipe-line structure.
2. The method for preparing the tube-wire type silicon-carbon negative electrode material according to claim 1, wherein in the step (1), the intermediate layer spinning solution is an emulsion formed by adding lecithin and deionized water into liquid paraffin, or a solution formed by adding PMMA or PVA into a mixed solution of acetone and DMF.
3. The preparation method of the tube-wire type structure silicon-carbon negative electrode material according to claim 2, characterized in that the mass of lecithin accounts for 5-12% of the mass of the middle layer spinning solution, and the mass of deionized water accounts for 2-5% of the mass of the middle layer spinning solution; the mass of PMMA or PVA accounts for 8-15% of the mass of the middle layer spinning solution, and the mass of acetone accounts for 20-40% of the mass of the middle layer spinning solution.
4. The preparation method of the tube-wire structure silicon-carbon anode material according to claim 1, wherein in the step (1), the mass of PAN accounts for 8-15% of the mass of the shell spinning solution; the mass of the silicon powder accounts for 5-10% of that of the core layer spinning solution, and the mass of the PAN accounts for 4-8% of that of the core layer spinning solution.
5. The method for preparing the silicon-carbon anode material with the pipe-line structure according to claim 4, wherein in the step (2), the inner diameter of the outer pipe is 1.64-1.94mm, the inner diameter of the middle pipe is 0.92-1.11mm, and the inner diameter of the inner pipe is 0.3-0.42 mm; the advancing rates of the shell layer spinning solution, the middle layer spinning solution and the core layer spinning solution are respectively 3-6 ml/h, 1-3 ml/h and 0.1-1 ml/h.
6. The method for preparing a silicon-carbon anode material with a pipe-line structure according to claim 1, wherein in the step (2), the relative humidity is 40% to 50%.
7. The method for preparing the silicon-carbon anode material with the pipe-line structure according to claim 1, wherein in the step (2), a spinneret is vertically arranged with a receiving plate, the applied voltage is 15-20 KV, the receiving distance is 15-20 cm, and the temperature is room temperature.
8. The method for preparing the silicon-carbon anode material with the pipe-line structure according to claim 1, wherein in the step (3), the pre-oxidation process comprises the following steps: pre-oxidizing for 1-3 h at 260-290 ℃ in air atmosphere, wherein the heating rate is 1-5 ℃/min.
9. The method for preparing the silicon-carbon anode material with the pipe-line structure according to claim 1, wherein in the step (3), the carbonization process comprises: carbonizing the mixture for 1-2 hours in a tubular furnace at 600-900 ℃ in an argon atmosphere, wherein the heating rate is 2-5 ℃/min.
10. A tube-line structured silicon carbon negative electrode material obtained by the method for preparing a tube-line structured silicon carbon negative electrode material according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011120103.3A CN112242513A (en) | 2020-10-19 | 2020-10-19 | Tube-wire structure silicon-carbon negative electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011120103.3A CN112242513A (en) | 2020-10-19 | 2020-10-19 | Tube-wire structure silicon-carbon negative electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112242513A true CN112242513A (en) | 2021-01-19 |
Family
ID=74169133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011120103.3A Pending CN112242513A (en) | 2020-10-19 | 2020-10-19 | Tube-wire structure silicon-carbon negative electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112242513A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113422009A (en) * | 2021-06-01 | 2021-09-21 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060019819A1 (en) * | 2004-07-23 | 2006-01-26 | Yang Shao-Horn | Fiber structures including catalysts and methods associated with the same |
| CN102234846A (en) * | 2010-04-28 | 2011-11-09 | 中国科学院化学研究所 | Core/shell fiber with nanowire-embedded microtube structure and preparation method thereof |
| CN104681787A (en) * | 2015-02-11 | 2015-06-03 | 浙江大学 | Self-supported silicon base anode material with multilayer thin film of lithium ion battery and preparation method thereof |
| WO2016198712A1 (en) * | 2015-06-08 | 2016-12-15 | Fundació Institut De Recerca En Energia De Catalunya | Nanostructures of concentric layers |
| CN106521705A (en) * | 2016-11-11 | 2017-03-22 | 吉林师范大学 | Preparation method of lithium battery anode material |
| CN108682802A (en) * | 2018-04-25 | 2018-10-19 | 福建翔丰华新能源材料有限公司 | A method of preparing lithium cell negative pole shell-core structure nanofiber |
-
2020
- 2020-10-19 CN CN202011120103.3A patent/CN112242513A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060019819A1 (en) * | 2004-07-23 | 2006-01-26 | Yang Shao-Horn | Fiber structures including catalysts and methods associated with the same |
| CN102234846A (en) * | 2010-04-28 | 2011-11-09 | 中国科学院化学研究所 | Core/shell fiber with nanowire-embedded microtube structure and preparation method thereof |
| CN104681787A (en) * | 2015-02-11 | 2015-06-03 | 浙江大学 | Self-supported silicon base anode material with multilayer thin film of lithium ion battery and preparation method thereof |
| WO2016198712A1 (en) * | 2015-06-08 | 2016-12-15 | Fundació Institut De Recerca En Energia De Catalunya | Nanostructures of concentric layers |
| EP3306685A1 (en) * | 2015-06-08 | 2018-04-11 | Fundacio Institut Recerca en Energia de Catalunya | Nanostructures of concentric layers |
| CN106521705A (en) * | 2016-11-11 | 2017-03-22 | 吉林师范大学 | Preparation method of lithium battery anode material |
| CN108682802A (en) * | 2018-04-25 | 2018-10-19 | 福建翔丰华新能源材料有限公司 | A method of preparing lithium cell negative pole shell-core structure nanofiber |
Non-Patent Citations (1)
| Title |
|---|
| YING LI等: "Coaxial electrospun Si/C-C core-shell composite nanofibers as binder-free anodes for lithium-ion batteries", 《SOLID STATE IONICS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113422009A (en) * | 2021-06-01 | 2021-09-21 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
| CN113422009B (en) * | 2021-06-01 | 2022-03-18 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109004265B (en) | Solid electrolyte positive electrode and solid battery comprising same | |
| CN108306013B (en) | Fast-charging and fast-discharging type high-power lithium ion battery and manufacturing method thereof | |
| CN110739485A (en) | low-temperature lithium ion batteries | |
| CN109713215B (en) | Lithium-supplement negative plate, preparation method thereof and lithium ion battery | |
| WO2016161920A1 (en) | Composite separator and preparation method therefor, and lithium-ion battery | |
| CN110364761B (en) | High-energy-density long-circulation lithium iron phosphate battery | |
| WO2016206548A1 (en) | Preparation method for lithium battery high-voltage modified negative electrode material | |
| CN111600064A (en) | Fast-charging lithium ion battery with high energy density and long service life and preparation method thereof | |
| CN110098387B (en) | Lithium phosphate and conductive carbon material coated ternary cathode material and preparation method and application thereof | |
| WO2018155746A1 (en) | Method for producing nickel-cobalt-manganese complex precursor with high specific surface area | |
| CN112635762B (en) | Lithium ion battery negative electrode material, preparation method and application thereof, and lithium ion battery | |
| CN112538692B (en) | Co-Mn bimetallic organic framework derived porous carbon fiber and preparation method and application thereof | |
| CN116826060B (en) | Composite sodium supplementing material, preparation method, positive pole piece, sodium battery and electric equipment | |
| CN114552122A (en) | Diaphragm, preparation method thereof and secondary battery | |
| CN112242513A (en) | Tube-wire structure silicon-carbon negative electrode material and preparation method thereof | |
| CN113725422B (en) | Silicon-carbon composite anode material, preparation method thereof and lithium ion battery | |
| CN114300650B (en) | In-situ spinning electrode slice, preparation method thereof and application thereof in lithium-sulfur battery | |
| CN115764010A (en) | Positive electrode lithium supplement agent, positive electrode lithium supplement pole piece prepared from positive electrode lithium supplement agent and lithium ion battery | |
| CN115148982A (en) | Composite positive electrode material, preparation method thereof, positive plate and battery | |
| CN111916704B (en) | Negative electrode material, preparation method, negative plate and battery | |
| CN108574096B (en) | NiO/rGO composite nano material, preparation method thereof and lithium battery anode material | |
| CN112467130A (en) | Long-life high-temperature lithium iron phosphate battery and preparation method thereof | |
| CN111333055A (en) | Preparation method of carbon nanotube doped lithium ion battery cathode material | |
| CN111769274A (en) | SiOx-C composite fiber felt negative electrode material and preparation method and application thereof | |
| CN116230911B (en) | High-power silicon-carbon negative electrode composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210119 |