WO2016208314A1 - リチウムイオン二次電池用負極活物質、およびリチウムイオン二次電池 - Google Patents
リチウムイオン二次電池用負極活物質、およびリチウムイオン二次電池 Download PDFInfo
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- WO2016208314A1 WO2016208314A1 PCT/JP2016/065372 JP2016065372W WO2016208314A1 WO 2016208314 A1 WO2016208314 A1 WO 2016208314A1 JP 2016065372 W JP2016065372 W JP 2016065372W WO 2016208314 A1 WO2016208314 A1 WO 2016208314A1
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- 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
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- 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
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- 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
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- H—ELECTRICITY
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- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a negative electrode active material for a lithium ion secondary battery and a lithium ion secondary battery.
- Graphite-based carbon materials are widely used as negative electrode active materials for lithium ion secondary batteries.
- the stoichiometric composition when graphite is filled with lithium ions is LiC 6 and its theoretical capacity can be calculated as 372 mAh / g.
- the stoichiometric composition when silicon is filled with lithium ions is Li 15 Si 4 or Li 22 Si 5 , and the theoretical capacity can be calculated as 3577 mAh / g or 4197 mAh / g.
- silicon is an attractive material that can store 9.6 times or 11.3 times as much lithium as graphite.
- the silicon particles are filled with lithium ions, the volume expands to about 2.7 times or 3.1 times, so that the silicon particles are dynamically destroyed during repeated filling and releasing of lithium ions.
- the silicon particles are broken, the broken fine silicon particles are electrically isolated, and a new electrochemical coating layer is formed on the broken surface, whereby the irreversible capacity is increased and the charge / discharge cycle characteristics are remarkably lowered.
- silicon particles nano-sized as a negative electrode active material of a lithium ion secondary battery By making silicon particles nano-sized as a negative electrode active material of a lithium ion secondary battery, mechanical breakdown associated with filling and releasing of lithium ions can be prevented. However, there has been a problem that due to the volume change accompanying the filling and releasing of lithium ions, some of the silicon nanoparticles are electrically isolated and the life characteristics are greatly deteriorated due to this.
- Patent Document 1 describes an example in which a Si metal thin film produced by a sputtering method is pulverized and applied to a negative electrode for a lithium ion secondary battery.
- the scaly Si particles obtained by pulverizing the Si metal thin film are likely to come into surface contact with each other, the particles are likely to become lumps.
- the Si-based active material has lower conductivity than the carbon material, the flaky Si active material that has become a problem particularly has a problem that the gap between the particles is small and the conductivity is lowered.
- An object of the present invention is to solve such problems and provide a negative electrode active material for a lithium ion secondary battery having a high capacity and a long life.
- the negative electrode is formed by applying the negative electrode mixture to a current collector, and the scaly silicon particles are a plurality of lithium ions that are overlapped on the current collector and are electrically bonded via a carbon layer. Secondary battery.
- a negative electrode active material for a lithium ion secondary battery that has excellent conductivity and can form a mixture layer even if it is scaly silicon particles, and has a high capacity and a long life.
- FIG. 1 is a diagram schematically showing a negative electrode active material for a lithium ion secondary battery according to an embodiment of the present invention.
- (A) is a top view
- (b) is a side sectional view.
- the carbon-coated flaky silicon particles 101 have a structure in which the carbon layer 103 is covered on the surface of the flaky silicon particles 102.
- the thickness of the scale-like silicon particles is 5 to 100 nm, more preferably 10 to 50 nm, and the longest diameter and longest diameter of the flat portion are 100 nm to 3 ⁇ m, and more preferably 100 nm to 1 ⁇ m.
- the thickness of the scaly silicon particles is 5 nm or less, the mechanical strength is weak, and there is a possibility of breaking into pieces during the negative electrode paste preparation process.
- the thickness is desirably 10 nm or more.
- the thickness is 100 nm or more, there is a high possibility of destruction due to volume expansion at the time of lithium ion filling.
- it is desirable that the thickness be 50 nm or less.
- the longest diameter is 100 nm or less, the shape is difficult to say a scale shape.
- the longest diameter is 3 ⁇ m or more, there is a high possibility of destruction due to volume expansion during lithium ion filling.
- the thickness is desirably 1 ⁇ m or less.
- the scaly silicon particles 101 need only have Si as an element, and may be Si, SiO 2 or an alloy of Si and another metal such as Ti, Cu, Al, or the like.
- the flaky silicon particles are apt to be lumped due to van der Waals force due to their flat shape.
- the scaly silicon particles have the carbon layer 103, the conductivity between the particles can be ensured.
- the scaly silicon particles can be produced, for example, by pulverizing a Si metal thin film produced on a substrate by sputtering. Further, after this, it is preferable to further process to a desired thickness and longest diameter using a planetary ball mill or a bead mill. By mixing with a ball mill, it can be processed to have a desired thickness and longest diameter, and further has an effect of separating particles.
- the carbon layer 103 has electrical conductivity and has an effect of improving electrical conduction between the scaly silicon particles 102. A certain effect can be expected even when the scaly silicon particles 102 are partially covered with the carbon layer 103 rather than the entire surface. Since the surface of the scaly silicon particles is oxidized in the atmosphere, it is covered with a natural oxide film having a thickness of about 2 nm. It is possible to form the carbon layer 103 on the natural oxide film or to form the carbon layer 103 directly on the silicon surface after removing the natural oxide film. From the viewpoint of reducing electrical resistance, it is desirable to remove the natural oxide film. The natural oxide film can be removed by heat treatment at 1000 ° C. in a hydrogen atmosphere, for example.
- a method for producing the carbon layer 103 will be described with reference to FIG. Place scaly silicon particles in a sample boat and install it near the center of the reactor.
- the reactor is made of quartz and has a diameter of 5 cm and a length of 40 cm.
- hydrogen gas was flowed at a flow rate of 200 mL / min, the growth furnace was heated from room temperature to 1000 ° C. at a rate of 10 ° C./min, and further maintained at 1000 ° C. for 1 hr.
- the natural oxide film formed on the surface of the scaly silicon particles can be reduced.
- the hydrogen line was closed, and argon gas was flowed at a flow rate of 200 mL / min, the temperature was lowered at a rate of 10 ° C./min, and the temperature was lowered to 800 ° C.
- propylene gas was introduced at a flow rate of 10 mL / min, and at the same time, the flow rate of argon gas was set to 190 mL / min, and the carbon coating layer was grown for 1 hour.
- the propylene gas line was closed, and argon gas was allowed to flow at a flow rate of 200 mL / min, maintained for 15 min, and then naturally cooled.
- the carbon layer itself is a multilayer nanographene layer in which nanographene is laminated in multiple layers, so that the carbon layer itself has excellent conductivity, and the mobility of electrons between scaly silicon particles is also high.
- the film thickness of the carbon layer can be set to any film thickness between 2 and 100 nm.
- the film thickness is 2 nm or less, the mechanical strength is weak, so there is a possibility of peeling due to the stress at the time of slurry preparation.
- the thickness is 100 nm or more, it is difficult to cover the scaly silicon particles with a uniform film thickness.
- the carbon layer has a structure in which nanographene is laminated in multiple layers, and has an electric conductivity of 1000 S / m or more.
- FIGS. 2 and 3 are scanning electron micrographs of scaly silicon particles. From the low-magnification photograph in FIG. 2, it can be seen that the average value of the longest and longest diameters of the flat portion of the scaly silicon particles is about 300 nm. Further, it can be seen from the high-magnification photograph in FIG. 3 that the thickness of the scaly silicon particles is about 20 nm.
- the scaly silicon particles are almost entirely covered.
- the coverage of the scaly silicon particles can be 90% or more. Due to the high coverage, conductivity can be ensured even when a plurality of scaly silicon layers overlap.
- there is a method of providing carbon by mixing conductive carbon with scaly silicon particles but in this case, the coverage is not as high as the above method.
- the mixing step for example, by mixing a bead mill or the like, the scaly silicon particles can be loosened and carbon can be interposed therebetween, which has the effect of increasing the conductivity between the silicon particles.
- FIG. 4 and 5 show scanning electron micrographs of scaly silicon particles coated with a carbon layer.
- 4 is a low-magnification photograph
- FIG. 5 is a high-magnification photograph.
- the carbon layer having a thickness of about 10 nm uniformly covers the surface of the scaly silicon particles.
- the carbon weight ratio was 9.9 wt%
- the silicon weight ratio was 90.1 wt%.
- the electric capacity can be adjusted by adjusting the amount of carbon coating on the scaly silicon surface described above.
- FIG. 7 shows the results of calculating the silicon weight ratio dependence of the electric capacity.
- the stoichiometric composition upon filling with lithium ions was assumed to be LiC 6 and its electric capacity was 372 mAh / g.
- the stoichiometric composition at the time of filling with lithium ions is assumed to be Li 15 Si 4 , assuming that its electric capacity is 3577 mAh / g, and Li 22 Si 5 , Calculation was made for the case where the electric capacity was 4197 mAh / g.
- Si of Si / (Si + C) is the weight of the scaly silicon particles
- C is the weight of the carbon layer or the like.
- 801 is a positive electrode
- 802 is a separator
- 803 is a negative electrode
- 804 is a battery can
- 805 is a positive current collector tab
- 806 is a negative current collector tab
- 807 is an inner lid
- 808 is an internal pressure release valve
- 809 is a gasket
- 810 is a positive temperature coefficient (TPC) resistance element
- 811 is a battery lid.
- the battery lid 811 is an integrated part including an inner lid 807, an internal pressure release valve 808, a gasket 809, and a positive temperature coefficient resistance element 810.
- the positive electrode 801 can be manufactured by the following procedure. LiMn 2 O 4 is used as the positive electrode active material. To 85.0 wt% of the positive electrode active material, 7.0 wt% and 2.0 wt% of graphite powder and acetylene black are added as conductive materials, respectively. Further, 6.0 wt% polyvinylidene fluoride (hereinafter abbreviated as PVDF) (a solution dissolved in 1-methyl-2-pyrrolidone (hereinafter abbreviated as NMP)) was added as a binder, and mixed with a planetary mixer. Further, air bubbles in the slurry are removed under vacuum to prepare a homogeneous positive electrode mixture slurry.
- PVDF polyvinylidene fluoride
- NMP 1-methyl-2-pyrrolidone
- This slurry is applied uniformly and evenly on both sides of an aluminum foil having a thickness of 20 ⁇ m using an applicator. After the application, compression molding is performed by a roll press so that the electrode density is 2.55 g / cm 3 . This is cut with a cutting machine to produce a positive electrode 801 having a thickness of 100 ⁇ m, a length of 900 mm, and a width of 54 mm.
- the negative electrode 803 can be manufactured by the following procedure.
- the negative electrode active material the above carbon-coated scale-like silicon particles can be used.
- a binder 5.0 wt% PVDF (solution dissolved in NMP) is added to 95.0 wt% of the negative electrode active material. It is mixed with a planetary mixer, and bubbles in the slurry are removed under vacuum to prepare a homogeneous negative electrode mixture slurry. This slurry is applied uniformly and evenly on both sides of a rolled copper foil having a thickness of 10 ⁇ m with an applicator. After coating, the electrode is compression-molded by a roll press machine so that the electrode density is 1.3 g / cm 3 .
- the negative electrode 803 is cut with a cutting machine to produce a negative electrode 803 having a thickness of 110 ⁇ m, a length of 950 mm, and a width of 56 mm.
- the negative electrode has a structure in which a negative electrode mixture is applied to a current collector, and a plurality of scaly silicon particles are in an electrically bonded state via a carbon layer on the current collector. For this reason, even if it is a material with high surface contact property like a scale-like silicon particle, electroconductivity is securable.
- negative electrode active materials can be used for the negative electrode mixture.
- a carbon-based active material such as graphite can be mixed.
- the positive electrode current collector tab 805 and the negative electrode current collector tab 806 are ultrasonically welded to the positive electrode 801 and the uncoated portion (current collector exposed surface) of the negative electrode 803, respectively.
- the positive electrode current collecting tab 805 can be an aluminum lead piece, and the negative electrode current collecting tab 806 can be a nickel lead piece.
- a separator 802 made of a porous polyethylene film having a thickness of 30 ⁇ m is inserted into the positive electrode 801 and the negative electrode 803, and the positive electrode 801, the separator 802, and the negative electrode 803 are wound.
- the wound body is accommodated in the battery can 804, and the negative electrode current collecting tab 806 is connected to the bottom of the battery can 804 by a resistance welding machine.
- the positive electrode current collecting tab 805 is connected to the bottom surface of the inner lid 807 by ultrasonic welding.
- the solvent of the electrolytic solution is composed of, for example, ethylene carbonate (EC), dimethyl carbonate (DMC), and diethyl carbonate (DEC), and has a volume ratio of 1: 1: 1.
- the electrolyte is LiPF 6 at a concentration of 1 mol / L (about 0.8 mol / kg). Such an electrolytic solution is dropped from above the wound body, and the battery lid 811 is caulked and sealed in the battery can 804, whereby a lithium ion secondary battery can be obtained.
- Example 1 For comparison, the life characteristics of a battery using flaky silicon particles not coated with carbon as a negative electrode material are also shown. Other conditions and the battery evaluation method were the same as in Example 1.
- FIG. 9 shows the life characteristics of a battery fabricated using the negative electrode material of the present invention.
- the capacity retention rate after 200 cycles was 97.0%, whereas the capacity retention rate of the scaly silicon particles not coated with carbon was 24.3%.
- Carbon-coated scaly silicon particles 102 scale-like silicon particles 103 carbon layer 801 positive electrode 802 Separator 803 negative electrode 804 battery can 805 Positive current collector tab 806 Negative electrode current collector tab 807 Inner lid 808 Pressure release valve 809 gasket, 810 Positive temperature coefficient resistance element 811 Battery cover
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Abstract
Description
図1は、本発明の一実施形態に係るリチウムイオン二次電池用負極活物質を模式的に表現した図である。(a)が上面図、(b)が側面断面図である。炭素被覆鱗片状シリコン粒子101は、鱗片状シリコン粒子102の表面に、炭素層103を被覆した構造を有する。鱗片状シリコン粒子の厚さが5~100nm、さらに望ましくは10~50nmであり、平坦部分の最も長い径、最長径が100nm~3μm、さらに望ましくは100nm~1μmである。鱗片状シリコン粒子の厚さが5nm以下の場合、機械的強度が弱く、負極ペースト作製工程中に粉々に破壊する可能性がある。十分な機械強度を確保するためには、その厚さが10nm以上であることが望ましい。また、その厚さが100nm以上になると、リチウムイオン充填時の体積膨張により破壊する可能性が高い。高速充放電時にも破壊しないためには、50nm以下であることが望ましい。また、最長径が100nm以下の場合、鱗片形状とは言い難い形状になってしまう。最長径が3μm以上になると、リチウムイオン充填時の体積膨張により破壊する可能性が高い。高速充放電時にも破壊しないためには、1μm以下であることが望ましい。
図7は、電気容量のシリコン重量比依存性を計算した結果である。炭素に対しては、リチウムイオンを充填した際の化学量論的組成を、LiC6と仮定し、その電気容量を372mAh/gとした。また、シリコンに対しては、リチウムイオンを充填した際の化学量論的組成を、Li15Si4と仮定し、その電気容量を3577mAh/gとした場合と、Li22Si5と仮定し、その電気容量を4197mAh/gとした場合について計算した。横軸のSi/(Si+C)のSiは、鱗片状シリコン粒子の重量を、Cは、炭素層等の重量である。シリコン重量比を変えることで、炭素固有の電気容量から、シリコン固有の電気容量まで、幅広く制御することが可能である。現実的には、シリコン重量比5~95wt%の複合材料を作製することが可能である。
本実施例では平均厚さは40nm、平均長径は300nmの鱗片状シリコン粒子101を作成した。また、その後、鱗片状シリコン粒子の表面の自然酸化膜を除去し、図6の方法により鱗片状シリコン粒子101に直接、厚さ5nmの炭素層を被覆した。最終的なシリコン重量比は90.1wt%であった。
上記の負極活物質を用いた電池を作成して、電池を評価した。
正極活物質の85.0wt%に、導電材として黒鉛粉末とアセチレンブラックをそれぞれ7.0wt%と2.0wt%を添加する。さらに、結着剤として6.0wt%のポリフッ化ビニリデン(以下、PVDFと略記)(1-メチル-2-ピロリドン(以下、NMPと略記)に溶解した溶液)を加えて、プラネタリ-ミキサーで混合し、さらに真空下でスラリー中の気泡を除去して、均質な正極合剤スラリーを調製する。このスラリーを、塗布機を用いて厚さ20μmのアルミニウム箔の両面に均一かつ均等に塗布する。塗布後ロールプレス機により電極密度が2.55g/cm3になるように圧縮成形する。これを切断機で裁断し、厚さ100μm、長さ900mm、幅54mmの正極801を作製する。
放電容量および維持率の測定は、1Cの速度で、定電流モードで行った。
比較のために、炭素被覆していない鱗片状シリコン粒子を負極材料として用いた電池の寿命特性も示した。その他の条件、電池の評価方法は実施例1と同様とした。
102 鱗片状シリコン粒子
103 炭素層
801 正極
802 セパレータ
803 負極
804 電池缶
805 正極集電タブ
806 負極集電タブ
807 内蓋
808 圧力開放弁
809 ガスケット、
810 正温度係数抵抗素子
811 電池蓋
Claims (8)
- 鱗片状のシリコン粒子を有するリチウムイオン二次電池用負極活物質であって、
前記鱗片状のシリコン粒子は、表面が炭素層により覆われているリチウムイオン二次電池用負極材料。 - 請求項1において、
前記炭素層は、ナノグラフェンが多層に積層した多層ナノグラフェン層であるリチウムイオン二次電池用負極材料。 - 請求項2において、
前記鱗片状シリコン粒子の厚さは5~100nmの範囲であるリチウムイオン二次電池用負極材料。 - 請求項3において、
平坦部分の最も長い径が100nm~3μmであるリチウムイオン二次電池用負極材料。 - 請求項4において、
前記鱗片状のシリコン粒子と前記炭素層の総量に対するシリコンの重量比は5~95wt%の範囲であるリチウムイオン二次電池用負極材料。 - 請求項5において、
前記炭素層の電気伝導率が1000S/m以上であるリチウムイオン二次電池用負極材料。 - 正極と負極とを有し、
前記負極は、負極合剤を有し、
前記負極合剤は、請求項1ないし請求項6のいずれかに記載のリチウムイオン二次電池用負極材料を有するリチウムイオン二次電池。 - 請求項7において、
前記負極は集電体に前記負極合剤が塗布されてなり、
前記鱗片状シリコン粒子は、前記集電体上で、複数重なり、
前記炭素層を介して、電気的に接合しているリチウムイオン二次電池。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2017524762A JPWO2016208314A1 (ja) | 2015-06-22 | 2016-05-25 | リチウムイオン二次電池用負極活物質、およびリチウムイオン二次電池 |
CN201680031626.6A CN107615528A (zh) | 2015-06-22 | 2016-05-25 | 锂离子二次电池用负极活性物质以及锂离子二次电池 |
US15/578,538 US20180159124A1 (en) | 2015-06-22 | 2016-05-25 | Negative electrode active material for lithium ion secondary batteries, and lithium ion secondary battery |
KR1020177034697A KR20180003577A (ko) | 2015-06-22 | 2016-05-25 | 리튬 이온 이차 전지용 부극 활물질 및 리튬 이온 이차 전지 |
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Cited By (4)
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WO2018131607A1 (ja) * | 2017-01-11 | 2018-07-19 | Jnc株式会社 | シリコンナノ粒子含有水素ポリシルセスキオキサン焼成物、リチウムイオン電池用負極活物質、リチウムイオン電池用負極、及びリチウムイオン電池 |
JP2018113187A (ja) * | 2017-01-12 | 2018-07-19 | 日立化成株式会社 | リチウムイオン二次電池用負極材料及びこれを用いたリチウムイオン二次電池 |
WO2018131608A1 (ja) * | 2017-01-11 | 2018-07-19 | Jnc株式会社 | ポリシルセスキオキサン被覆シリコンナノ粒子又はその焼成物及びその製造方法、リチウムイオン電池用負極活物質、リチウムイオン電池用負極、及びリチウムイオン電池 |
WO2018131606A1 (ja) * | 2017-01-11 | 2018-07-19 | Jnc株式会社 | シリコンナノ粒子含有水素ポリシルセスキオキサン焼成物-金属酸化物複合体及びその製造方法、リチウムイオン電池用負極活物質、リチウムイオン電池用負極、及びリチウムイオン電池 |
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CN110197895A (zh) * | 2018-02-26 | 2019-09-03 | 华为技术有限公司 | 一种复合材料及其制备方法 |
CN109935808A (zh) * | 2019-02-27 | 2019-06-25 | 福建翔丰华新能源材料有限公司 | 一种基于微米硅片制备硅碳负极材料的方法 |
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US20180159124A1 (en) | 2018-06-07 |
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