WO2022193286A1 - 负极材料及其制备方法、电化学装置及电子装置 - Google Patents

负极材料及其制备方法、电化学装置及电子装置 Download PDF

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WO2022193286A1
WO2022193286A1 PCT/CN2021/081795 CN2021081795W WO2022193286A1 WO 2022193286 A1 WO2022193286 A1 WO 2022193286A1 CN 2021081795 W CN2021081795 W CN 2021081795W WO 2022193286 A1 WO2022193286 A1 WO 2022193286A1
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negative electrode
electrode material
carbon fiber
silicon
porous carbon
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French (fr)
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姜道义
陈志焕
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to PCT/CN2021/081795 priority Critical patent/WO2022193286A1/zh
Priority to CN202180030956.4A priority patent/CN115443559B/zh
Publication of WO2022193286A1 publication Critical patent/WO2022193286A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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

Definitions

  • the present application relates to the technical field of anode materials, and in particular, to anode materials and preparation methods thereof, electrochemical devices and electronic devices.
  • silicon-based anode materials have a gram capacity as high as 1500mAh/g to 4200mAh/g, and are considered to be the most promising next-generation lithium-ion anode materials.
  • silicon due to the low electrical conductivity of silicon (>10 8 ⁇ .cm), and its volume expansion of about 300% during charge-discharge and the formation of an unstable solid electrolyte interface (SEI), the silicon anode material in the charge-discharge process It will be pulverized and dropped from the current collector, causing the loss of electrical contact between the active material and the current collector, resulting in poor electrochemical performance, capacity attenuation, and cycle stability, which hinders its further application to a certain extent.
  • SEI solid electrolyte interface
  • Nano-sized silicon-based anode materials and dispersed in carbon matrix can effectively improve the cycle performance of silicon-based anode materials. After granulation, carbonization is carried out to obtain the silicon-carbon composite material that is mainly used now. However, the cycle performance of this anode material is low and the expansion rate is relatively large.
  • the present application proposes a negative electrode material and a preparation method thereof, an electrochemical device and an electronic device.
  • the negative electrode material can effectively alleviate the expansion of the negative electrode due to the expansion of the silicon base and graphite, thereby improving the cycle performance of the negative electrode material.
  • the present application provides a negative electrode material
  • the negative electrode material includes a porous carbon fiber skeleton and a silicon-based material filled inside the porous carbon fiber skeleton; wherein the porous carbon fiber skeleton has a diameter of 0.5um to 5um, and The aspect ratio of the porous carbon fiber skeleton is 5 to 100.
  • the negative electrode material further includes a carbon layer.
  • the thickness of the carbon layer is 1 nm to 100 nm.
  • the negative electrode material satisfies at least one of the following conditions (1) to (4):
  • the mass percentage content of silicon in the negative electrode material is 5% to 50%;
  • the mass percentage content of carbon in the negative electrode material is 50% to 95%
  • the specific surface area of the negative electrode material is less than 50 m 2 /g
  • the powder true density of the negative electrode material is 2.0 g/cm 3 to 2.3 g/cm 3 .
  • the highest intensity value of the diffraction peak attributable to 28.4° ⁇ 0.2° is M, which is attributable to 45° ⁇ 0.5°.
  • the highest intensity value of the diffraction peak is N, where M/N ⁇ 1.
  • an embodiment of the present application provides a method for preparing a negative electrode material, the method comprising the following steps:
  • the mixed solution is prepared into a polymer fiber of 0.2um to 10um by a spinning process
  • the diameter of the porous carbon fiber skeleton is 0.5um to 5um, and the aspect ratio of the porous carbon fiber skeleton is 5 to 100;
  • a carbon source gas is passed into the silicon-loaded carbon fiber material to carry out secondary vapor deposition to obtain the negative electrode material.
  • the present application provides a negative electrode sheet, comprising a negative electrode current collector and a negative electrode active material layer disposed on the surface of the negative electrode current collector, the negative electrode active material layer comprising the negative electrode material described in the first aspect or the second negative electrode material layer.
  • the present application provides an electrochemical device, comprising a negative electrode active material layer, the negative electrode active material layer comprising the negative electrode material described in the first aspect or the negative electrode material prepared by the method for preparing the negative electrode material described in the second aspect .
  • the electrochemical device is a lithium-ion battery.
  • the present application provides an electronic device comprising the electrochemical device of the fourth aspect.
  • the present application at least has the following beneficial effects:
  • the negative electrode material provided by the present application by controlling the size of the porous carbon fiber skeleton and the aspect ratio of the porous carbon fiber skeleton, the silicon-based material is deposited into the porous carbon fiber skeleton, and the porous carbon fiber skeleton is used as the supporting skeleton of the negative electrode material.
  • the pores can alleviate a certain volume expansion, and the fibrous support skeleton can effectively increase the long-range electrical contact of the silicon-based negative electrode material relative to the granular carbon skeleton, which can effectively alleviate the expansion of the negative electrode due to the expansion of the silicon-based material and the graphite. Improve the cycle performance of anode active materials.
  • any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with any other lower limit to form an unspecified range, and likewise any upper limit can be combined with any other upper limit to form an unspecified range.
  • every point or single value between the endpoints of a range is included within the range, even if not expressly recited.
  • each point or single value may serve as its own lower or upper limit in combination with any other point or single value or with other lower or upper limits to form a range not expressly recited.
  • an embodiment of the present application provides a negative electrode material, the negative electrode material includes a porous carbon fiber skeleton and a silicon-based material filled inside the porous carbon fiber skeleton; wherein the porous carbon fiber skeleton has a diameter of 0.5 ⁇ m to 5um, and the aspect ratio of the porous carbon fiber skeleton is 5 to 100.
  • the negative electrode material provided by the present application by controlling the size of the porous carbon fiber skeleton and the aspect ratio of the porous carbon fiber skeleton, the silicon-based material is deposited into the porous carbon fiber skeleton, and the porous carbon fiber skeleton is used as the supporting skeleton of the negative electrode material.
  • the pores can alleviate a certain volume expansion, and the fibrous support skeleton can effectively increase the long-range electrical contact of the silicon-based negative electrode relative to the granular skeleton, which can effectively alleviate the expansion of the negative electrode due to the expansion of the silicon-based material and the graphite, thereby improving the negative electrode. Cycling performance of active materials.
  • the diameter of the porous carbon fiber skeleton can be specifically 0.5um, 0.7um, 1.4um, 1.5um, 1.6um, 3.2um, 5.0um, etc., of course, it can also be within the above range. Other values are not limited here.
  • the aspect ratio of the porous carbon fiber skeleton can be specifically 5, 5.5, 6.4, 6.6, 6.9, 7.0, 8.0, 12.8, 13, 20, 50, or 100, and of course can also be other values within the above range, which is not specified here. Do limit. When the diameter of the porous carbon fiber skeleton is too large, the aspect ratio will be too small. If the aspect ratio is too small, there will be fewer contact sites between the silicon composite material and the graphite. In the process of silicon expansion, it is easy to cause silicon The electrical contact with the graphite fails, thereby deteriorating the cycle performance of the cell.
  • the highest intensity value of the diffraction peak attributable to 28.4° ⁇ 0.2° is M
  • the highest intensity value of the diffraction peak attributable to 45° ⁇ 0.5° is M.
  • the value is N, where M/N ⁇ 1.
  • the diffraction peak attributable to the vicinity of 28.4° is the diffraction peak formed by silicon particles of crystalline silicon
  • the diffraction peak attributable to the vicinity of 45° is the diffraction peak formed by carbon
  • the carbon peak is used as a reference to limit the silicon peak growth.
  • the negative electrode material further includes a carbon layer, and the thickness of the carbon layer is 1 nm to 100 nm. It is understandable that if the carbon layer is too thick, the lithium ion transmission efficiency is reduced, which is not conducive to the high-rate charge and discharge of the material, and the comprehensive performance of the negative electrode material is reduced. Weak performance, resulting in poor performance for long loops.
  • the thickness of the carbon layer is 1 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm or 100 nm, etc.
  • it can also be other values within the above range, which is not limited here. .
  • the mass percentage content of silicon element in the negative electrode material is 5% to 50%; %, etc., but are not limited to the recited values, and other unrecited values within the numerical range are also applicable. If the silicon content is too high, the volume expansion rate of the lithium-ion battery will increase, which is not conducive to improving the cycle stability; if the silicon content is too low, the first effect and rate performance of the lithium-ion battery will be affected.
  • the mass percentage content of carbon element in the negative electrode material is 50% to 95%; %, etc., but are not limited to the recited values, and other unrecited values within the numerical range are also applicable. If the carbon content is too high, the lithium ion transmission efficiency is reduced, which is not conducive to the high-rate charge and discharge of the material, and the comprehensive performance of the negative electrode material is reduced. Weak, resulting in long-cycle performance spreads.
  • the specific surface area of the negative electrode material is less than 50m 2 /g; specifically, it can be 1.50m 2 /g, 2.00m 2 /g, 5.0m 2 /g, 10.0m 2 /g, 15m 2 /g, 20m 2 /g, 30m 2 /g or 40m 2 /g, etc., but are not limited to the recited values, and other unrecited values within the range of values are also applicable.
  • the specific surface area of the negative electrode material is within the above range, which ensures the processing performance of the material, is conducive to improving the primary efficiency of the lithium battery made of the negative electrode material, and is conducive to improving the cycle performance of the negative electrode material.
  • the specific surface area of the negative electrode material is 2.6 m 2 /g to 28 m 2 /g, and further preferably, the specific surface area of the negative electrode material is 2.6 m 2 /g to 5.2 m 2 /g.
  • the true powder density of the negative electrode material is 2.0 g/cm 3 to 2.3 g/cm 3 . Specifically, it can be 2.0g/cm 3 , 2.05g/cm 3 , 2.1g/cm 3 , 2.15g/cm 3 , 2.2g/cm 3 , 2.25g/cm 3 or 2.3g/cm 3 , etc., but not Not limited to the recited values, other non-recited values within this range of values are equally applicable.
  • the true density of the negative electrode material is within the above range, which is beneficial to improve the energy density of the lithium battery made of the negative electrode material.
  • the true density of the above-mentioned powder is to place a certain mass of powder samples in a true density tester, close the test system, and pass helium or nitrogen into the test system according to the program.
  • the true volume so as to calculate the true density of the powder.
  • the present application provides a method for preparing a negative electrode material, the method comprising the following steps:
  • the mixed solution is prepared into a polymer fiber of 0.2um to 10um by a spinning process
  • the diameter of the porous carbon fiber skeleton is 0.5um to 5um, and the aspect ratio of the porous carbon fiber skeleton is 5 to 100;
  • a silicon source gas is introduced into the porous carbon fiber skeleton, and a vapor deposition is performed to obtain a silicon-loaded carbon fiber material;
  • a carbon source gas is passed into the silicon-loaded carbon fiber material to carry out secondary vapor deposition to obtain the negative electrode material.
  • silicon is deposited into the porous carbon fiber skeleton by thermal decomposition of the silicon source gas.
  • the fibrous carbon skeleton can effectively increase the long-range electrical contact of the silicon-based negative electrode material, which can effectively alleviate the The expansion of the silicon base and graphite leads to the expansion of the negative electrode, which can effectively improve the cycle performance of the negative electrode active material.
  • Step S10 the porogen and acrylonitrile are dispersed in dimethylacrylamide to form a mixed solution.
  • the porogen is calcium carbonate, and the particle size of the calcium carbonate particles is 10 nm to 20 nm. Specifically, it can be 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm or 20 nm, and of course other values within the above range are also possible.
  • the porogen can adhere to the polymer fibers, and then through the acid washing treatment, a porous structure is formed.
  • the molecular weight of the acrylonitrile is 100w to 1000w; specifically, it can be 100w, 150w, 200w, 300w, 400w, 500w, 600w, 700w, 800w or 1000w, etc., of course, it can also be in the above range other values within.
  • step S20 the mixed solution is prepared into a polymer fiber of 0.2 um to 10 um by a spinning process.
  • the spinning process includes at least one of electrospinning, liquid-phase spinning, and melt spinning.
  • Step S30 carbonizing, crushing and pickling the polymer fibers to obtain the porous carbon fiber skeleton, the diameter of the porous carbon fiber skeleton is 0.5um to 5um, and the aspect ratio of the porous carbon fiber skeleton is 5 to 100.
  • the long-range electrical contact of the silicon-based anode material can be effectively increased, the expansion of the anode caused by the expansion of the silicon-based and graphite can be effectively alleviated, and the cycle performance of the anode active material can be effectively improved.
  • the steps of the carbonization treatment include:
  • the polymer fibers are oxidized in air at 200°C to 300°C for 2h to 10h, and then placed in an argon atmosphere at 600°C to 1200°C for high temperature carbonization for 2h to 12h.
  • the acrylonitrile can undergo a ring-forming reaction, which is beneficial to the formation of a more stable carbon fiber material after heat treatment.
  • the polymer fibers are carbonized to form carbon fibers, and the carbon fibers can be used as the skeleton structure of the negative electrode active material, which can improve the cycle stability of the negative electrode active material.
  • the crushing treatment includes at least one of ball milling, wet sand milling or high-speed jet milling. It can be understood that the crushing process can obtain carbon fiber materials of different lengths, and further control the aspect ratio of the porous carbon fiber skeleton.
  • the acid solution used in the pickling treatment is hydrochloric acid or hydrofluoric acid. It can be understood that hydrochloric acid or hydrofluoric acid can react with the porogen attached to the carbon fiber, so that the porogen can be dissolved in the hydrochloric acid or hydrofluoric acid, so that the carbon fiber forms a pore structure.
  • the porogen is nanoscale particles, the pore structure formed on the carbon fiber is also nanoscale.
  • step S40 a silicon source gas is introduced into the porous carbon fiber skeleton, and a vapor deposition is performed to obtain a silicon-loaded carbon fiber material;
  • one vapor deposition is silicon deposition, and silicon is deposited into the carbon fiber skeleton to form nano-silicon. Since the pore structure of the carbon fiber is also nano-scale, the silicon aggregation area on the carbon fiber skeleton can be effectively controlled to be less than 20 nm, and the nano-pore structure can be effectively controlled. It can also alleviate the volume expansion of silicon, thereby improving the cycling performance of silicon-based materials.
  • the silicon source gas is silane.
  • the deposition temperature of the primary vapor deposition is 500°C to 900°C, specifically 500°C, 550°C, 600°C, 650°C, 700°C, 800°C or 900°C, etc.
  • 500°C, 550°C, 600°C, 650°C, 700°C, 800°C or 900°C is 500°C to 900°C, specifically 500°C, 550°C, 600°C, 650°C, 700°C, 800°C or 900°C, etc.
  • Other values within the above ranges are also possible.
  • the deposition time of the primary vapor deposition is 0.25h to 24h; specifically, it may be 0.25h, 0.5h, 1h, 2h, 3h, 6h, 8h, 12h, 16h, 18h or 24h, etc. , of course other values within the above range are also possible.
  • step S50 a carbon source gas is introduced into the silicon-loaded carbon fiber material, and secondary vapor deposition is performed to obtain the negative electrode material.
  • the carbon source gas includes at least one of methane, acetylene, propane or ethylene.
  • the deposition temperature of the secondary vapor deposition is 500°C to 950°C, specifically 500°C, 550°C, 600°C, 650°C, 700°C, 800°C, 900°C or 950°C
  • °C the deposition temperature of the secondary vapor deposition
  • the deposition time of the secondary vapor deposition is 0.5h to 12h; specifically, it can be 0.5h, 1h, 2h, 3h, 6h, 8h, 10h or 12h, etc., of course, it can also be the above-mentioned other values in the range.
  • an embodiment of the present application provides a negative electrode sheet, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector, the negative electrode active material layer comprises the negative electrode active material layer according to the first aspect of the present application negative electrode material.
  • the negative electrode active material layer includes a binder
  • the binder includes polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylic The (esterified) styrene-butadiene rubber, epoxy resin, nylon, etc., are not limited here.
  • the negative electrode active material layer further includes a conductive material
  • the conductive material includes natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, metal powder, metal fiber, copper, nickel, aluminum , silver or polyphenylene derivatives, etc., are not limited here.
  • the negative electrode current collector includes, but is not limited to, copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, foamed copper or a polymer substrate coated with conductive metal.
  • the present application further provides an electrochemical device, comprising a negative electrode active material layer, the negative electrode active material layer comprising the negative electrode material described in the first aspect or the method for preparing the negative electrode material described in the second aspect above. obtained negative electrode material.
  • the electrochemical device further includes a positive electrode plate, and the positive electrode plate includes a positive electrode current collector and a positive electrode active material layer located on the positive electrode current collector.
  • the positive active material includes at least one of lithium cobalt oxide (LiCoO2), lithium nickel manganese cobalt ternary material, lithium iron phosphate, lithium manganese iron phosphate, and lithium manganate.
  • LiCoO2 lithium cobalt oxide
  • LiN lithium nickel manganese cobalt ternary material
  • iron phosphate lithium manganese iron phosphate
  • manganate lithium manganate
  • the positive electrode active material layer further includes a binder and a conductive material.
  • the binder improves the bonding of the positive electrode active material particles to each other, and also improves the bonding of the positive electrode active material to the current collector.
  • the binder includes polyvinyl alcohol, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinylpyrrolidone , at least one of polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylic (esterified) styrene-butadiene rubber, epoxy resin or nylon.
  • the conductive material includes carbon-based materials, metal-based materials, conductive polymers, and mixtures thereof.
  • the carbon-based material is selected from natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, or any combination thereof.
  • the metal-based material is selected from metal powders, metal fibers, copper, nickel, aluminum, or silver.
  • the conductive polymer is a polyphenylene derivative.
  • the positive electrode current collector includes, but is not limited to, aluminum foil.
  • the electrochemical device further includes an electrolyte, and the electrolyte includes an organic solvent, a lithium salt and an additive.
  • the organic solvent of the electrolytic solution according to the present application may be any organic solvent known in the prior art that can be used as a solvent of the electrolytic solution.
  • the electrolyte used in the electrolyte solution according to the present application is not limited, and it may be any electrolyte known in the prior art.
  • the additive for the electrolyte according to the present application may be any additive known in the art as an additive for the electrolyte.
  • the organic solvent includes, but is not limited to: ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), propylene carbonate or ethyl propionate.
  • the lithium salt includes at least one of an organic lithium salt or an inorganic lithium salt.
  • the lithium salts include, but are not limited to: lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium difluorophosphate (LiPO 2 F 2 ), bistrifluoromethanesulfonimide Lithium LiN(CF 3 SO 2 ) 2 (LiTFSI), Lithium Bis(fluorosulfonyl)imide Li(N(SO 2 F) 2 )(LiFSI), Lithium Bisoxalate Borate LiB(C 2 O 4 ) 2 (LiBOB) ) or lithium difluorooxalate borate LiBF 2 (C 2 O 4 ) (LiDFOB).
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • LiPO 2 F 2 lithium difluorophosphate
  • LiPFSI bistrifluoromethanesulfonimide Lithium LiN(CF 3 SO
  • the concentration of the lithium salt in the electrolyte may be 0.5 mol/L to 3 mol/L.
  • the electrochemical device of the present application includes, but is not limited to: all kinds of primary batteries, secondary batteries, fuel cells, solar cells or capacitors.
  • the electrochemical device is a lithium secondary battery, wherein the lithium secondary battery includes, but is not limited to, a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion secondary battery polymer secondary battery.
  • an embodiment of the present application further provides an electronic device, where the electronic device includes the electrochemical device described in the fourth aspect.
  • the electronic devices include, but are not limited to: notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets, etc. stereo headphones, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power, motors, cars, motorcycles, power Bicycles, bicycles, lighting equipment, toys, game consoles, clocks, power tools, flashlights, cameras, large household batteries or lithium-ion capacitors, etc.
  • lithium-ion batteries The preparation of lithium-ion batteries is described below by taking lithium-ion batteries as an example and combining with specific examples.
  • the mixed solution is prepared into a polymer fiber of 0.2um to 10um by a spinning process
  • the polymer fibers are oxidized in air at 250°C for 5 hours, then carbonized at high temperature, and sintered at 1000°C for 8 hours in an inert atmosphere, and then crushed and pickled to obtain a porous carbon fiber skeleton;
  • Examples 1 to 9 were prepared according to the above method, and the specific parameters of Examples 1 to 9 are shown in Table 1 below.
  • Comparative Example 1 was prepared according to the above method.
  • the aspect ratio of the prepared porous carbon fiber skeleton of Comparative Example 1 was 1.0.
  • the specific parameters of Comparative Example 1 are shown in Table 1 below.
  • the selected test instrument was: OXFORD EDS (X-max-20mm 2 ), the acceleration voltage was 10KV to adjust the focus, and the observation magnification was from 50K for high magnification observation and low magnification. From 500 to 2000, the particle agglomeration is mainly observed.
  • the adsorption amount of the sample monolayer is calculated based on the Brownnauer-Etter-Taylor adsorption theory and its formula (BET formula), and then calculate The specific surface area of a solid.
  • the sample is heated and burned at high temperature in a high-frequency furnace under oxygen-rich conditions to oxidize carbon and sulfur into carbon dioxide and sulfur dioxide. .
  • This signal is sampled by the computer, converted into a value proportional to the concentration of carbon dioxide and sulfur dioxide after linear correction, and then the value of the whole analysis process is accumulated. After the analysis, the accumulated value is divided by the weight value in the computer, and then multiplied by Correction coefficient, subtract the blank, you can obtain the percentage of carbon and sulfur in the sample.
  • Samples were tested using a high-frequency infrared carbon-sulfur analyzer (Shanghai Dekai HCS-140).
  • the positive active material lithium cobalt oxide (LiCoO 2 ), conductive carbon black, and binder polyvinylidene fluoride are mixed according to the weight ratio of 95:2.5:2.5, and N-methylpyrrolidone (NMP) is added.
  • NMP N-methylpyrrolidone
  • the negative electrode materials, graphite, conductive agent (conductive carbon black, Super ) and binder PAA are mixed according to the weight ratio of 70:15:5:10, deionized water is added, and the negative electrode slurry is obtained under the action of a vacuum mixer; the negative electrode slurry is uniformly coated on the negative electrode current collector copper foil; The copper foil is dried, then subjected to cold pressing, cutting and slitting, and then dried under vacuum conditions to obtain a negative electrode sheet.
  • a polyethylene porous polymer film is used as the separator.
  • the positive electrode, the separator and the negative electrode in order, so that the separator is placed between the positive and negative electrode sheets to isolate them, and then wind them to obtain a bare cell; after welding the tabs, place the bare cell on the outer packaging foil aluminum
  • the above-prepared electrolyte is injected into the dried bare cell, and the lithium-ion battery is obtained through the processes of vacuum packaging, standing, chemical formation, shaping, and capacity testing.
  • the lithium-ion battery that has reached a constant temperature is charged with a constant current of 0.7C to a voltage of 4.4V, and then charged with a constant voltage of 4.4V to a current of 0.025C. After standing for 5 minutes, it is discharged with a constant current of 0.5C to a voltage of 3.0V.
  • the capacity obtained in this step is the initial capacity, and 0.7C charge/0.5C discharge is carried out for cycle test, and the capacity decay curve is obtained by taking the ratio of the capacity in each step to the initial capacity.
  • the room temperature cycle performance of the battery was recorded as the number of cycles from 25°C to 90% of the capacity retention rate, and the number of cycles from 45°C to 80% of the capacity retention rate was recorded as the high-temperature cycle performance of the battery.
  • the number of cycles in each case compares the cycle performance of the materials.
  • the lithium-ion battery that has reached a constant temperature is discharged with a constant current of 0.2C to a voltage of 3.0V, left for 5 minutes, charged with a constant current of 0.5C to a voltage of 4.45V, and then charged with a constant voltage of 4.45V to a current of 0.05C and then left to stand. 5min, adjust the discharge rate, conduct the discharge test at 0.2C, 0.5C, 1C, 1.5C, 2.0C, respectively, to obtain the discharge capacity, and compare the capacity obtained at each rate with the capacity obtained at 0.2C. The ratio at 0.2C compares rate performance.
  • the gram capacity in this application form is the gram capacity with a discharge cut-off voltage of 2.0V;
  • the first efficiency calculation method in this application form is the capacity corresponding to the discharge cut-off voltage of 2.0V/the capacity corresponding to the charge voltage cut-off to 0.005V.
  • Example 1 500 5.3% 420 6.0%
  • Example 2 480 5.8% 390 6.2%
  • Example 3 450 6.2%
  • Comparative Example 1 380 6.4% 350 7.2%
  • the mass percentage content of silicon in the negative electrode material is 17.2% to 39%.
  • the diameter of the porous carbon fiber skeleton adopted in Example 4 is 1.5um
  • the diameter of the porous carbon fiber skeleton adopted in Example 5 is 3.2um
  • the The diameter of the carbon fiber skeleton is 5.1 um
  • the aspect ratio of the porous carbon fiber skeleton of Examples 4 to 6 is in the range of 5.4 to 6.9
  • the silicon content and carbon content of the negative electrode material are similar. It can be seen that when the diameter of the porous carbon fiber skeleton is greater than 5um, the cyclability of the lithium-ion battery will decrease instead. Therefore, the diameter of the porous carbon fiber skeleton should be controlled to be 0.5um to 5um.

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Abstract

本申请提供了负极材料及其制备方法、电化学装置及电子装置，其中，所述负极材料包括多孔碳纤维骨架以及填充于所述多孔碳纤维骨架内部的硅基材料；其中，所述多孔碳纤维骨架的直径为0.5um至5um，且所述多孔碳纤维骨架的长径比为5至100。本申请提供的负极材料可以有效缓解由于硅基与石墨膨胀导致负极的膨胀，从而改善负极材料的循环性能。

Description

负极材料及其制备方法、电化学装置及电子装置 技术领域
本申请涉及负极材料技术领域，具体地讲，涉及负极材料及其制备方法、电化学装置及电子装置。
背景技术
目前，硅基负极材料具有高达1500mAh/g至4200mAh/g的克容量，被认为是最具有应用前景的下一代锂离子负极材料。但是硅的低电导性(>10 8Ω.cm)，以及其在充放电过程中具有约300％的体积膨胀并生成不稳定的固体电解质界面膜(SEI)，硅负极材料在充放电过程中会粉化从集流体上掉落，使得活性物质与集流体之间失掉电触摸，导致电化学性能变差，容量衰减、循环稳定性下降，一定程度上阻碍了其进一步的应用。将硅基负极材料进行纳米化并分散在碳基体中可以有效改善硅基负极材料的循环性能，例如可以通过将硅采用湿法研磨的方式球磨至100nm左右，进而与沥青，聚合物等进行造粒后碳化，从而得到现在主要应用的硅碳复合材料。但是，这种负极材料的循环性能较低，膨胀率也相对较大。
申请内容
鉴于此，本申请提出了负极材料及其制备方法、电化学装置及电子装置，该负极材料可以有效缓解由于硅基与石墨膨胀导致负极的膨胀，从而改善负极材料的循环性能。
第一方面，本申请提供一种负极材料，所述负极材料包括多孔碳纤维骨架以及填充于所述多孔碳纤维骨架内部的硅基材料；其中，所述多孔碳纤维骨架的直径为0.5um至5um，且所述多孔碳纤维骨架的长径比为5至100。
结合第一方面，在一种可行的实施方式中，所述负极材料还包含有碳层。
结合第一方面，在一种可行的实施方式中，所述碳层的厚度为1nm至100nm。
结合第一方面，在一种可行的实施方式中，所述负极材料满足以下条件(1)至(4)中的至少一者：
(1)所述负极材料中的硅的质量百分比含量为5％至50％；
(2)所述负极材料中的碳的质量百分比含量为50％至95％；
(3)所述负极材料的比表面积小于50m 2/g；
(4)所述负极材料的粉末真密度为2.0g/cm 3至2.3g/cm 3。
结合第一方面，在一种可行的实施方式中，所述负极材料在X射线衍射图谱中，归属于28.4°±0.2°的衍射峰的最高强度值为M，归属于45°±0.5°的衍射峰的最高强度值为N，其中，M/N≥1。
第二方面，本申请实施例提供一种负极材料的制备方法，所述方法包括以下步骤：
将致孔剂和丙烯腈分散在二甲基丙烯酰胺中形成混合溶液；
将所述混合溶液通过纺丝工艺制备成0.2um至10um的聚合纤维；
将所述聚合物纤维进行碳化、破碎及酸洗处理，得到多孔碳纤维骨架，所述多孔碳纤维骨架的直径为0.5um至5um，且所述多孔碳纤维骨架的长径比为5至100；
往所述多孔碳纤维骨架内通入硅源气体，进行一次气相沉积，得到负载硅的碳纤维材料；
往所述负载硅的碳纤维材料内通入碳源气体，进行二次气相沉积，得到所述负极材料。
第三方面，本申请提供一种负极极片，包括负极集流体以及设置于所述负极集流体表面的负极活性材料层，所述负极活性材料层包括第一方面所述的负极材料或第二方面所述的负极材料制备方法制得的负极材料。
第四方面，本申请提供一种电化学装置，包括负极活性材料层，所述负极活性材料层包括第一方面所述的负极材料或第二方面所述的负极材料制备方法制得的负极材料。
结合第四方面，在一种可行的实施方式中，所述电化学装置为锂离子电池。
第五方面，本申请提供一种电子装置，所述电子装置包括第四方面所述的电化学装置。
相对于现有技术，本申请至少具有以下有益效果：
本申请提供的负极材料，通过控制多孔碳纤维骨架的尺寸和多孔碳纤维骨架的长径比，将硅基材料沉积到多孔碳纤维骨架中，利用多孔碳纤维骨架作为负极材料的支撑骨架，多孔碳纤维骨架的内部孔隙可以缓解一定的体积膨胀，并且纤维状的支撑骨架相对于颗粒状的碳骨架可以有效增加了硅基负极材料的长程电接触，可以有效缓解由于硅基材料与石墨膨胀导致负极的膨胀，从而改善负极活性材料的循环性能。
具体实施方式
以下所述是本申请实施例的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本申请实施例的保护范围。
为了简便，本文仅明确地公开了一些数值范围。然而，任意下限可以与任何上限组合形成未明确记载的范围；以及任意下限可以与其它下限组合形成未明确记载的范围，同样任意上限可以与任意其它上限组合形成未明确记载的范围。此外，尽管未明确记载，但是范围端点间的每个点或单个数值都包含在该范围内。因而，每个点或单个数值可以作为自身的下限或上限与任意其它点或单个数值组合或与其它下限或上限组合形成未明确记载的范围。
在本文的描述中，需要说明的是，除非另有说明，“以上”、“以下”为包含本数，“一种或多种”中“多种”的含义是两个以上。
本申请的上述申请内容并不意欲描述本申请中的每个公开的实施方式或每种实现方式。如下描述更具体地举例说明示例性实施方式。在整篇申请中的多处，通过一系列实施例提供了指导，这些实施例可以以各种组合形式使用。在各个实例中，列举仅 作为代表性组，不应解释为穷举。
第一方面，本申请实施例提供了一种负极材料，所述负极材料包括多孔碳纤维骨架以及填充于所述多孔碳纤维骨架内部的硅基材料；其中，所述多孔碳纤维骨架的直径为0.5um至5um，且所述多孔碳纤维骨架的长径比为5至100。
本申请提供的负极材料，通过控制多孔碳纤维骨架的尺寸和多孔碳纤维骨架的长径比，将硅基材料沉积到多孔碳纤维骨架中，利用多孔碳纤维骨架作为负极材料的支撑骨架，多孔碳纤维骨架的内部孔隙可以缓解一定的体积膨胀，并且纤维状的支撑骨架相对于颗粒状的骨架可以有效增加了硅基负极的长程电接触，可以有效缓解由于硅基材料与石墨膨胀导致负极的膨胀，从而改善负极活性材料的循环性能。
作为本申请可选的技术方案，所述多孔碳纤维骨架的直径具体可以是0.5um、0.7um、1.4um、1.5um、1.6um、3.2um、5.0um等等，当然也可以是上述范围内的其他值，在此不做限定。所述多孔碳纤维骨架的长径比具体可以是5、5.5、6.4、6.6、6.9、7.0、8.0、12.8、13、20、50或100，当然也可以是上述范围内的其他值，在此不做限定。当所述多孔碳纤维骨架的直径过大时，会导致长径比过小，长径比过小会导致硅的复合材料与石墨的接触位点较少，在硅膨胀过程中，很容易造成硅与石墨的电接触失效，从而恶化电芯的循环性能。
作为本申请可选的技术方案，所述负极材料在X射线衍射图谱中，归属于28.4°±0.2°的衍射峰的最高强度值为M，归属于45°±0.5°的衍射峰的最高强度值为N，其中，M/N≥1。
需要说明的是，归属于28.4°附近的衍射峰为晶体硅的硅微粒形成的衍射峰，归属于45°附近的衍射峰为碳形成的衍射峰；通过以碳的峰作为参比以限制硅的峰的增长。
作为本申请可选的技术方案，所述负极材料还包含有碳层，所述碳层的厚度为1nm至100nm。可以理解地，碳层过厚，锂离子传输效率降低，不利于材料大倍率充放电，降低负极材料的综合性能，碳层过薄，不利于增加负极材料的导电性且对材料的体积膨胀抑制性能较弱，导致长循环性能较差。
可选地，所述碳层的厚度为1nm、5nm、10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm或100nm等，当然也可以是上述范围内的其他值，在此不做限定。
作为本申请可选的技术方案，所述负极材料中的硅元素的质量百分比含量为5％至50％；具体可以是5％、15％、20％、25％、30％、40％或50％等等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。硅元素含量过高，锂离子电池体积膨胀率上升，不利于提高循环稳定性；硅元素含量过低，影响锂离子电池的首效及倍率性能。
作为本申请可选的技术方案，所述负极材料中的碳元素的质量百分比含量为50％至95％；具体可以是50％、55％、60％、65％、70％、80％或95％等等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。碳元素含量过高，锂离子传输效率降低，不利于材料大倍率充放电，降低负极材料的综合性能，碳元素含量过低，不利于增加负极材料的导电性且对材料的体积膨胀抑制性能较弱，导致长循环性能价差。
作为本申请可选的技术方案，所述负极材料的比表面积小于50m 2/g；具体可以是1.50m 2/g、2.00m 2/g、5.0m 2/g、10.0m 2/g、15m 2/g、20m 2/g、30m 2/g或40m 2/g等等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。所述负极材料的比表面积在上述范围内，保证了材料的加工性能，有利于提高由该负极材料制成的锂电池的首次效率，有利于提高负极材料的循环性能。优选地，所述负极材料的比表面积为2.6m 2/g至28m 2/g，进一步优选地，所述负极材料的比表面积为2.6m 2/g至5.2m 2/g。
作为本申请可选的技术方案，所述负极材料的粉末真密度为2.0g/cm 3至2.3g/cm 3。具体可以是2.0g/cm 3、2.05g/cm 3、2.1g/cm 3、2.15g/cm 3、2.2g/cm 3、2.25g/cm 3或2.3g/cm 3，等等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。所述负极材料的真密度在上述范围内，有利于提高由该负极材料制成的锂电池的能量密度。上述粉末真密度是将一定质量的粉末样品置于真密度测试仪，密闭测试系统，按照程序通入氦气或氮气，通过测试样品室和膨胀室中气体的压力，在根据波尔定律计算出真实体积，从而计算得到粉末真密度。
第二方面，本申请提供一种负极材料的制备方法，所述方法包括以下步骤：
将致孔剂和丙烯腈分散在二甲基丙烯酰胺中形成混合溶液；
将所述混合溶液通过纺丝工艺制备成0.2um至10um的聚合纤维；
将所述聚合物纤维进行碳化、破碎及酸洗处理，得到所述多孔碳纤维骨架，所述多孔碳纤维骨架的直径为0.5um至5um，且所述多孔碳纤维骨架的长径比为5至100；
往多孔碳纤维骨架内通入硅源气体，进行一次气相沉积，得到负载硅的碳纤维材料；
往所述负载硅的碳纤维材料内通入碳源气体，进行二次气相沉积，得到所述负极材料。
在上述方案中，采用硅源气体热分解的方式将硅沉积到多孔碳纤维骨架中，纤维状的碳骨架相对于颗粒状的碳骨架可以有效增加硅基负极材料的长程电接触，可以有效缓解由于硅基与石墨膨胀导致负极的膨胀，可以有效改善负极活性材料的循环性能。
以下结合实施例具体介绍本制备方法：
步骤S10，将致孔剂和丙烯腈分散在二甲基丙烯酰胺中形成混合溶液。
在具体实施例中，所述致孔剂为碳酸钙，所述碳酸钙颗粒的粒径为10nm至20nm。具体可以是10nm、11nm、12nm、13nm、14nm、15nm、16nm、17nm、18nm或20nm，当然也可以是上述范围内的其他值。通过控制致孔剂的粒径，使得致孔剂能够粘附于聚合物纤维上，再通过酸洗处理，形成多孔结构。
作为本申请可选的技术方案，所述丙烯腈的分子量为100w至1000w；具体可以是100w、150w、200w、300w、400w、500w、600w、700w、800w或1000w等，当然也可以是上述范围内的其他值。
步骤S20，将所述混合溶液通过纺丝工艺制备成0.2um至10um的聚合纤维。
作为本申请可选的技术方案，所述纺丝工艺包括静电纺丝、液相纺丝、熔融纺丝中的至少一种。
步骤S30，将所述聚合物纤维进行碳化、破碎及酸洗处理，得到所述多孔碳纤维骨架，所述多孔碳纤维骨架的直径为0.5um至5um，且所述多孔碳纤维骨架的长径比为5至100。
通过控制孔碳纤维材料的长径比，可以有效增加硅基负极材料的长程电接触，可以有效缓解由于硅基与石墨膨胀导致负极的膨胀，可以有效改善负极活性材料的循环性能。
具体地，所述碳化处理的步骤包括：
将所述聚合物纤维置于200℃至300℃空气中氧化2h至10h后，再置于600℃至1200℃氩气环境下进行高温碳化2h至12h。
在氧化过程中，可以使得丙烯腈发生成环反应，有利于热处理后形成更加稳定的碳纤维材料。
在高温碳化过程中，聚合物纤维碳化形成碳纤维，碳纤维可以作为负极活性材料的骨架结构，能够提高负极活性材料的循环稳定性。
作为本申请可选的技术方案，所述破碎处理包括球磨、湿法砂磨或高速气流磨中的至少一种。可以理解地，破碎处理能够得到不同长度的碳纤维材料，进而控制多孔碳纤维骨架的长径比。
作为本申请可选的技术方案，所述酸洗处理所采用的酸溶液为盐酸或氢氟酸。可以理解地，盐酸或氢氟酸能够与附着于碳纤维上的致孔剂发生反应，使得致孔剂能够溶于盐酸或氢氟酸，使得碳纤维形成孔结构。在本实施例中，由于致孔剂为纳米级颗粒，形成于碳纤维上的孔结构也呈纳米级。
步骤S40，往多孔碳纤维骨架内通入硅源气体，进行一次气相沉积，得到负载硅的碳纤维材料；
可以理解地，一次气相沉积为硅沉积，将硅沉积到碳纤维骨架中形成纳米硅，由于碳纤维的孔结构也呈纳米级，可以有效控制碳纤维骨架上的硅聚集区在20nm以下，并且纳米孔结构还能缓解硅的体积膨胀，从而改善硅基材料的循环性能。在本实施例中，所述硅源气体为硅烷。
作为本申请可选的技术方案，所述一次气相沉积的沉积温度为500℃至900℃，具体可以是500℃、550℃、600℃、650℃、700℃、800℃或900℃等，当然也可以是上述范围内的其他值。
作为本申请可选的技术方案，所述一次气相沉积的沉积时间为0.25h至24h；具体可以是0.25h、0.5h、1h、2h、3h、6h、8h、12h、16h、18h或24h等，当然也可以是上述范围内的其他值。
步骤S50，往所述负载硅的碳纤维材料内通入碳源气体，进行二次气相沉积，得到所述负极材料。
作为本申请可选的技术方案，所述碳源气体包括甲烷、乙炔、丙烷或乙烯中的至少一种。
作为本申请可选的技术方案，所述二次气相沉积的沉积温度为500℃至950℃，具体可以是500℃、550℃、600℃、650℃、700℃、800℃、900℃或950℃等，当然也可以是上述范围内的其他值。
作为本申请可选的技术方案，所述二次气相沉积的沉积时间为0.5h至12h；具体可以是0.5h、1h、2h、3h、6h、8h、10h或12h等，当然也可以是上述范围内的其他值。
第三方面，本申请实施例提供了一种负极极片，所述负极极片包括负极集流体和位于负极集流体上的负极活性材料层，所述负极活性材料层包括根据本申请第一方面的负极材料。
作为本申请可选的技术方案，负极活性材料层包括粘合剂，粘合剂包括聚乙烯醇、羧甲基纤维素、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂或尼龙等，在此不做限定。
作为本申请可选的技术方案，负极活性材料层还包括导电材料，导电材料包括天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维、金属粉、金属纤维、铜、镍、铝、银或聚亚苯基衍生物等，在此不做限定。
作为本申请可选的技术方案，负极集流体包括，但不限于：铜箔、镍箔、不锈钢箔、钛箔、泡沫镍、泡沫铜或覆有导电金属的聚合物基底。
第四方面，本申请还提供了一种电化学装置，包括负极活性材料层，所述负极活性材料层包括上述第一方面所述的负极材料或上述第二方面所述的负极材料制备方法制得的负极材料。
作为本申请可选的技术方案，电化学装置还包括正极极片，正极极片包括正极集流体和位于正极集流体上的正极活性材料层。
作为本申请可选的技术方案，正极活性材料包括钴酸锂(LiCoO2)、锂镍锰钴三元材料、磷酸铁锂、磷酸锰铁锂、锰酸锂中的至少一种。
作为本申请可选的技术方案，正极活性材料层还包括粘合剂和导电材料。可以理解地，粘合剂提高正极活性材料颗粒彼此间的结合，并且还提高正极活性材料与集流体的结合。
具体地，粘合剂包括聚乙烯醇、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧化的聚氯乙烯、聚氟乙烯、含亚乙基氧的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏1,1-二氟乙烯、聚乙烯、聚丙烯、丁苯橡胶、丙烯酸(酯)化的丁苯橡胶、环氧树脂或尼龙中的至少一种。
具体地，导电材料包括基于碳的材料、基于金属的材料、导电聚合物和它们的混合物。在一些实施例中，基于碳的材料选自天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维或其任意组合。在一些实施例中，基于金属的材料选自金属粉、金属纤维、铜、镍、铝或银。在一些实施例中，导电聚合物为聚亚苯基衍生物。
作为本申请可选的技术方案，正极集流体包括，但不限于：铝箔。
作为本申请可选的技术方案，电化学装置还包括电解液，所述电解液包括有机溶剂、锂盐和添加剂。
根据本申请的电解液的有机溶剂可为现有技术中已知的任何可作为电解液的溶剂 的有机溶剂。根据本申请的电解液中使用的电解质没有限制，其可为现有技术中已知的任何电解质。根据本申请的电解液的添加剂可为现有技术中已知的任何可作为电解液添加剂的添加剂。
在具体实施例中，所述有机溶剂包括，但不限于：碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸二甲酯(DMC)、碳酸亚丙酯或丙酸乙酯。
在具体实施例中，所述锂盐包括有机锂盐或无机锂盐中的至少一种。
在具体实施例中，所述锂盐包括，但不限于：六氟磷酸锂(LiPF 6)、四氟硼酸锂(LiBF 4)、二氟磷酸锂(LiPO 2F 2)、双三氟甲烷磺酰亚胺锂LiN(CF 3SO 2) 2(LiTFSI)、双(氟磺酰)亚胺锂Li(N(SO 2F) 2)(LiFSI)、双草酸硼酸锂LiB(C 2O 4) 2(LiBOB)或二氟草酸硼酸锂LiBF 2(C 2O 4)(LiDFOB)。
在具体实施例中，所述电解液中锂盐的浓度可以为0.5mol/L至3mol/L。
作为本申请可选的技术方案，本申请的电化学装置包括，但不限于：所有种类的一次电池、二次电池、燃料电池、太阳能电池或电容。
在具体实施例中，所述电化学装置是锂二次电池，其中，锂二次电池包括，但不限于：锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。
第五方面，本申请实施例还提供一种电子装置，电子装置包括上述第四方面所述的电化学装置。
作为本申请可选的技术方案，所述电子装置包括，但不限于：笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池或锂离子电容器等。
下面以锂离子电池为例并且结合具体的实施例说明锂离子电池的制备，本领域的
技术人员将理解，本申请中描述的制备方法仅是实例，其他任何合适的制备方法均在本申请的范围内。
一、负极材料的制备
将粒径为10nm至20nm的碳酸钙和丙烯腈分散在二甲基丙烯酰胺中形成混合溶液；
将所述混合溶液通过纺丝工艺制备成0.2um至10um的聚合纤维；
将所述聚合物纤维置于250℃空气中氧化5h后进行高温碳化，在惰性气氛下置于1000℃烧结8h后进行破碎及酸洗处理，得到多孔碳纤维骨架；
往多孔碳纤维骨架内通入硅烷气体，进行一次气相沉积，控制沉积温度为500℃至900℃，沉积时间为0.25h至24h，得到负载硅的碳纤维材料；
往所述负载硅的碳纤维材料内通入乙烯气体，进行二次气相沉积，控制沉积温度为500℃至950℃，沉积时间为0.5h至12h，得到所述负极材料，其中碳层的厚度为 1nm至100nm。
根据上述方法制备实施例1至9，实施例1至9的具体参数见下表1。
进一步地，根据上述方法制备对比例1，对比例1的制成的多孔碳纤维骨架的长径比为1.0，对比例1的具体参数见下表1。
进一步地，根据上述方法制备对比例2，对比例2的制备过程中，混合溶液没有采纺丝工艺制成聚合纤维，而是制成块状聚合物，制成的负极材料中的碳骨架呈球形状。对比例2的具体参数见下表1。
表1.碳骨架性能参数
Figure PCTCN2021081795-appb-000001
二、负极材料的性能测试：
(1)负极材料粉末颗粒微观形貌观察：
利用扫面电镜进行粉末微观形貌观察表征材料表面情况，所选测试仪器为：OXFORD EDS(X-max-20mm 2),加速电压为10KV调整焦距，观测倍数从50K进行高倍观察，低倍下500至2000主要观察颗粒团聚情况。
(2)多孔碳纤维骨架的直径测试方法：
采用SEM随机挑选20根纤维，测试纤维的直接和长度，得到每根纤维的长度和长度，将所述纤维的直径取均值，即得到纤维的直径，长度取均值即得到纤维的长度，将二者进行比值得到纤维的长径比。
(3)负极材料中硅含量的测试方法:
称取0.05至0.1g样品加入1.2至1.5g的干燥的氢氧化钾，放入马弗炉中400℃，冷却后加入沸水浸湿后，反复清洗干过，用中速滤纸将样品溶液过滤至100mL的PP瓶中并定容后，然后稀释100倍后，采用ICP-OES测试稀释液，然后计算出样品的硅含量。
(4)负极材料比表面积的测试方法:
在恒温低温下，测定不同相对压力时的气体在固体表面的吸附量后，基于布朗诺尔-埃特-泰勒吸附理论及其公式(BET公式)求得试样单分子层吸附量，从而计算出固体的比表面积。
称取约1.5g至3.5g粉末样品装入TriStar II 3020的测试样品管中，约200℃脱气120min后进行测试。
(5)负极材料真密度的测试方法:
称取一定质量的样品(1g至5g)，置于真密度测试仪，密闭测试系统，按照程序通入氦气或者氮气。通过测试样品室和膨胀室中的气体的压力，再根据波尔定律(PV＝nRT)计算出真实体积，从而计算出真密度。
(6)负极材料中碳含量的测试方法:
样品在富氧条件下由高频炉高温加热燃烧使碳、硫氧化成二氧化碳、二氧化硫，该气体经处理后进入相应的吸收池，对相应的红外辐射进行吸收再由探测器转化成对应的信号。此信号由计算机采样，经线性校正后转换成与二氧化碳、二氧化硫浓度成正比的数值，然后把整个分析过程的取值累加，分析结束后，此累加值在计算机中除以重量值，再乘以校正系数，扣除空白，即可获得样品中碳、硫百分含量。利用高频红外碳硫分析仪(上海徳凯HCS-140)进行样品测试。
(7)负极材料的X射线衍射测试：
称取样品1.0g至2.0g倒入玻璃样品架的凹槽内，并用玻璃片将其压实和磨平，采用X射线衍射仪(布鲁克，D8)按照JJS K 0131-1996《X射线衍射分析法通则》进行测试，测试电压设置40kV，电流为30mA，扫描角度范围为10°至85°，扫描步长为0.0167°，每个步长所设置的时间为0.24s，得到负极材料的XRD衍射图案，从XRD衍射图案中得到中2θ归属于28.4°最高强度值M，与归属于45°最高强度值N，从而计算出M/N的比值。
三、锂电池的制备
(1)正极的制备
将正极活性材料钴酸锂(LiCoO 2)、导电炭黑、粘结剂聚偏二氟乙烯按照重量比95：2.5：2.5进行混合，加入N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌均匀，获得正极浆料；将正极浆料均匀涂覆于正极集流体铝箔上；将铝箔烘干，然后经过冷压、裁片、分切后，在真空条件下干燥，得到正极片。
(2)负极的制备
将上述实施例以及对比例的负极材料、石墨、导电剂(导电炭黑、Super
Figure PCTCN2021081795-appb-000002
)和粘结剂PAA按照重量比70：15：5：10进行混合，加入去离子水，在真空搅拌机作用下获得负极浆料；将负极浆料均匀涂覆在负极集流体铜箔上；将铜箔烘干，然后经过冷压、裁片、分切后，在真空条件下干燥，得到负极片。
(3)电解液
在干燥的氩气气氛手套箱中，往碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)(重量比约1：1：1)混合而成的溶剂中，加入LiPF6混合均匀，其中LiPF6的浓度为约1.15mol/L，混合均匀得到电解液。
(4)隔离膜
以聚乙烯多孔聚合薄膜作为隔离膜。
(5)锂离子电池的制备
将正极、隔离膜、负极按顺序叠好，使隔离膜处于正、负极片之间起到隔离的作用，然后卷绕得到裸电芯；焊接极耳后将裸电芯置于外包装箔铝塑膜中，将上述制备好的电解液注入到干燥后的裸电芯中，经过真空封装、静置、化成、整形、容量测试等工序，获得锂离子电池。
四、锂电池的性能测试：
(1)锂离子电池循环性能测试
将锂离子电池置于45℃(25℃)恒温箱中，静置30分钟，使锂离子电池达到恒温。将达到恒温的锂离子电池以0.7C恒流充电至电压为4.4V，然后以4.4V恒压充电至电流为0.025C，静置5分钟后以0.5C恒流放电至电压为3.0V，以此步骤得到的容量为初始容量，进行0.7C充电/0.5C放电进行循环测试，以每一步的容量与初始容量做比值，得到容量衰减曲线。以25℃循环截至到容量保持率为90％的圈数记为电池的室温循环性能，以45℃循环截至到容量保持率为80％的圈数记为电池的高温循环性能，通过比较上述两种情况下的循环圈数比较材料的循环性能。
(2)放电倍率测试：
将锂离子电池置于25℃恒温箱中，静置30分钟，使锂离子电池达到恒温。将达到恒温的锂离子电池以0.2C恒流放电至电压为3.0V，静置5min，以0.5C恒流充电到电压为4.45V，然后以4.45V恒压充电到电流为0.05C后静置5min，调整放电倍率，分别以0.2C、0.5C、1C、1.5C、2.0C进行放电测试，分别得到放电容量，以每个倍率下得到的容量与0.2C得到的容量对比，通过比较2C与0.2C下的比值比较倍率性能。
(3)电池满充膨胀率测试：
用螺旋千分尺测试半充(50％充电状态(SOC))时新鲜电池的厚度，循环至400圈时，电池处于满充(100％SOC)状态下，再用螺旋千分尺测试此时电池的厚度，与初始半充(50％SOC)时新鲜电池的厚度对比，即可得此时满充(100％SOC)电池膨胀率。
根据上述方法制得的实施例1至3的负极材料及对比例1的负极材料性能参数见表1-1，其制得的锂电池的性能测试结果见表1-2所示。
表1-1
Figure PCTCN2021081795-appb-000003
需要说明的是，本申请表中的克容量是放电截至电压为2.0V的克容量；
本申请表中的首次效率计算方式为放电截至电压为2.0V的容量/充电电压截至到0.005V对应的容量。
表1-2
样本 25℃循环截至到90％ 25℃循环至400圈的 45℃循环截至到90％ 45℃循环至400圈的
  的圈数 电池膨胀率 的圈数 电池膨胀率
实施例1 500 5.3％ 420 6.0％
实施例2 480 5.8％ 390 6.2％
实施例3 450 6.2％ 380 6.9％
对比例1 380 6.4％ 350 7.2％
从实施例1至3的测试结果可以看出，当采用同一类型的碳纤维骨架时，随着沉积在碳纤维骨架上的硅含量的增加，实施例1至3的负极材料的克容量也逐步上升，电池的首效也有所提升。但是电池的循环性能随着硅含量的上升有所下降，电池膨胀率也上升了；由此可见，需要控制负极材料的硅含量。优选地，所述负极材料中的硅的质量百分比含量为17.2％至39％。
而对比例1采用球形的碳骨架颗粒，锂电池的循环性能相较于实施例1至3明显下降，膨胀效率明显上升。这是因为碳纤维骨架相比于球形的碳骨架颗粒，能够有效增加负极材料的长程电接触，可以缓解由于硅与石墨导致负极的膨胀，从而改善负极材料的循环性能。
根据上述方法制得的实施例4至6的负极材料及对比例1的负极材料性能参数见表2-1，其制得的锂电池的性能测试结果见表2-2所示。
表2-1
Figure PCTCN2021081795-appb-000004
表2-2
Figure PCTCN2021081795-appb-000005
从实施例4至6的测试结果可以看出，实施例4所采用的多孔碳纤维骨架的直径为1.5um，实施例5所采用的多孔碳纤维骨架的直径为3.2um，实施例6所采用的多孔碳纤维骨架的直径为5.1um，且实施例4至6的多孔碳纤维骨架的长径比在5.4至6.9范围内，负极材料的硅含量及碳含量相近。由此可见，当多孔碳纤维骨架的直径大于5um时，锂离子电池循环性反而会下降。因此，所述多孔碳纤维骨架的直径应该控制为0.5um至5um。
根据上述方法制得的实施例7至9的负极材料及对比例2的负极材料性能参数见表3-1，其制得的锂电池的性能测试结果见表3-2所示。
表3-1
Figure PCTCN2021081795-appb-000006
表3-2
Figure PCTCN2021081795-appb-000007
从实施例7至9的测试结果可以看出，当多孔碳纤维骨架的直径为0.5um至5um，且所述多孔碳纤维骨架的长径比为5至100时，锂离子电池具有良好的循环性能和倍率性能，以及较低的膨胀率。由对比例2采用碳纤维骨架，其长径比小于5时，锂离子电池的循环性能和倍率性能较差，且膨胀率较高。
本申请虽然以较佳实施例公开如上，但并不是用来限定权利要求，任何本领域技术人员在不脱离本申请构思的前提下，都可以做出若干可能的变动和修改，因此本申请的保护范围应当以本申请权利要求所界定的范围为准。

Claims (15)

  1. 一种负极材料，其特征在于，所述负极材料包括多孔碳纤维骨架以及填充于所述多孔碳纤维骨架内部的硅基材料；其中，所述多孔碳纤维骨架的直径为0.5um至5um，且所述多孔碳纤维骨架的长径比为5至100。
  2. 根据权利要求1所述的负极材料，其特征在于，所述负极材料还包含有碳层。
  3. 根据权利要求2所述的负极材料，其特征在于，所述碳层的厚度为1nm至100nm。
  4. 根据权利要求1所述的负极材料，其特征在于，所述负极材料满足以下条件(1)至(4)中的至少一者：
    (1)所述负极材料中的硅元素的质量百分比含量为5％至50％；
    (2)所述负极材料中的碳元素的质量百分比含量为50％至95％；
    (3)所述负极材料的比表面积小于50m 2/g；
    (4)所述负极材料的粉末真密度为2.0g/cm 3至2.3g/cm 3。
  5. 根据权利要求1所述的负极材料，其特征在于，所述负极材料在X射线衍射图谱中，归属于28.4°±0.2°的衍射峰的最高强度值为M，归属于45°±0.5°的衍射峰的最高强度值为N，其中，M/N≥1。
  6. 一种负极材料的制备方法，其特征在于，所述方法包括以下步骤：
    将致孔剂和丙烯腈分散在二甲基丙烯酰胺中形成混合溶液；
    将所述混合溶液通过纺丝工艺制备成0.2um至10um的聚合纤维；
    将所述聚合物纤维进行碳化、破碎及酸洗处理，得到多孔碳纤维骨架，所述多孔碳纤维骨架的直径为0.5um至5um，且所述多孔碳纤维骨架的长径比为5至100；
    往所述多孔碳纤维骨架内通入硅源气体，进行一次气相沉积，得到负载硅的碳纤维材料；
    往所述负载硅的碳纤维材料内通入碳源气体，进行二次气相沉积，得到所述负极材料。
  7. 根据权利要求6所述的制备方法，其特征在于，所述负极材料满足以下条件(1)至(5)中的至少一者：
    (1)所述负极材料中的硅元素的质量百分比含量为5％至50％；
    (2)所述负极材料中的碳元素的质量百分比含量为50％至95％；
    (3)所述负极材料的比表面积小于50m 2/g；
    (4)所述负极材料的粉末真密度为2.0g/cm 3至2.3g/cm 3；
    (5)所述负极材料的碳层的厚度为1nm至100nm。
  8. 根据权利要求6所述的制备方法，其特征在于，所述方法满足以下条件(6)至(7)中的至少一者：
    (6)所述一次气相沉积的沉积温度为500℃至900℃，沉积时间为0.25h至24h；
    (7)所述硅源气体为硅烷。
  9. 根据权利要求6所述的制备方法，其特征在于，所述方法满足以下条件(8)至(9)中的至少一者：
    (8)所述二次气相沉积的沉积温度为500℃至950℃，沉积时间为0.5h至12h；
    (9)所述碳源气体包括甲烷、乙炔、丙烷或乙烯中的至少一种。
  10. 根据权利要求6所述的制备方法，其特征在于，所述方法满足以下条件(10)至(12)中的至少一者：
    (10)所述碳化处理的条件包括将所述聚合物纤维置于200℃至300℃空气中氧化2h至10h后，再置于600℃至1200℃进行高温碳化2h至12h；
    (11)所述破碎处理包括球磨、湿法砂磨或高速气流磨中的至少一种；
    (12)所述酸洗处理所采用的酸溶液为盐酸或氢氟酸。
  11. 根据权利要求6所述的制备方法，其特征在于，所述方法满足以下条件(13)至(15)中的至少一者：
    (13)所述致孔剂为碳酸钙，所述碳酸钙颗粒的粒径为10nm至20nm；
    (14)所述丙烯腈的分子量为100w至1000w；
    (15)所述纺丝工艺包括静电纺丝、液相纺丝、熔融纺丝中的至少一种。
  12. 一种负极极片，包括负极集流体以及设置于所述负极集流体表面的负极活性材料层，其特征在于，所述负极活性材料层包括权利要求1至5中任一项所述的负极材料或权利要求6至11中任一项所述的负极材料制备方法制得的负极材料。
  13. 一种电化学装置，包括负极活性材料层，其特征在于，所述负极活性材料层包括权利要求1至5中任一项所述的负极材料或权利要求6至11中任一项所述的负极材料制备方法制得的负极材料。
  14. 根据权利要求13所述的电化学装置，其特征在于，所述电化学装置为锂离子电池。
  15. 一种电子装置，其特征在于，所述电子装置包括权利要求13所述的电化学装置。
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WO2025081751A1 (zh) * 2023-10-20 2025-04-24 宁德时代新能源科技股份有限公司 硅碳复合材料及其制备方法、二次电池和用电装置
CN117438558A (zh) * 2023-10-23 2024-01-23 柔电（武汉）科技有限公司 一种硅碳负极及其制备方法
CN117438558B (zh) * 2023-10-23 2024-05-24 柔电（武汉）科技有限公司 一种硅碳负极及其制备方法
CN118173860A (zh) * 2024-03-31 2024-06-11 宁德新能源科技有限公司 一种二次电池和电子装置
WO2025241601A1 (zh) * 2024-05-20 2025-11-27 华为技术有限公司 负极材料及其制备方法、负极、电池、电子设备及储能设备
CN118693270A (zh) * 2024-08-23 2024-09-24 至华新能源科技(浙江)有限公司 一种长循环硅碳负极材料及其制备方法
CN119601624A (zh) * 2024-11-28 2025-03-11 四川紫宸科技有限公司 一种硅碳负极材料及其制备方法、负极片和锂离子电池
CN119601624B (zh) * 2024-11-28 2025-10-03 四川紫宸科技有限公司 一种硅碳负极材料及其制备方法、负极片和锂离子电池
CN121416409A (zh) * 2025-12-30 2026-01-27 深圳众诚达应用材料股份有限公司 一种负极片及其制备方法和固态电池

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