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WO2018176254A1 - Matériau actif d'électrode, anode et batterie contenant ledit matériau actif d'électrode et procédé de fabrication d'une batterie - Google Patents

Matériau actif d'électrode, anode et batterie contenant ledit matériau actif d'électrode et procédé de fabrication d'une batterie Download PDF

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Publication number
WO2018176254A1
WO2018176254A1 PCT/CN2017/078550 CN2017078550W WO2018176254A1 WO 2018176254 A1 WO2018176254 A1 WO 2018176254A1 CN 2017078550 W CN2017078550 W CN 2017078550W WO 2018176254 A1 WO2018176254 A1 WO 2018176254A1
Authority
WO
WIPO (PCT)
Prior art keywords
sodium
active material
electrode active
lithium
anode
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.)
Ceased
Application number
PCT/CN2017/078550
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English (en)
Inventor
Xiaogang HAO
Rongrong JIANG
Lei Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Priority to CN201780089129.6A priority Critical patent/CN110462890B/zh
Priority to PCT/CN2017/078550 priority patent/WO2018176254A1/fr
Publication of WO2018176254A1 publication Critical patent/WO2018176254A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/049—Processes for forming or storing electrodes in the battery container
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Definitions

  • the present invention relates to an electrode active material for lithium ion batteries, which contains granular porous silicon or silicon alloy, and sodium ions, wherein the sodium ions are intercalated into the granular porous silicon or silicon alloy.
  • the present invention also relates to an anode containing said electrode active material, and to a lithium-ion battery containing said anode.
  • the present invention further relates to a method for preparing a lithium-ion battery.
  • Silicon is a promising candidate anode material owing to its high theoretical specific capacity of 4200 mAh/g for Li 4.4 Si. Nevertheless, two issues are considered to be critical to realize its application. One is the volume change during the charging and discharging processes, which causes cracking and crumbling of the electrode material, and consequently loss of electrical contact between individual silicon particles and a severe capacity drop. The other is the property of the surface layer on Si in contact with the electrolyte, also known as the solid-electrolyte-interface (SEI) .
  • SEI solid-electrolyte-interface
  • the object of the present invention is solve the following problems: volume change during the charging and discharging processes, poor Li + conductivity, and poor electronic conductivity.
  • an electrode active material for lithium ion batteries which contains granular porous silicon or silicon alloy, and sodium ions, wherein the sodium ions are intercalated into the granular porous silicon or silicon alloy.
  • an anode which contains the electrode active material according to the present invention.
  • a lithium-ion battery which contains the anode according to the present invention.
  • Said object can be achieved by a method for preparing a lithium-ion battery, said method including the following steps:
  • FIGS. 1 ⁇ 3 are schematic drawings of the formation process of the method according to the present invention.
  • Figure 4 shows the cycling performances of the lithium-ion batteries of Example 1 (E1) , Example 2 (E2) , Example 3 (E3) , and Comparative Example (CE) .
  • the present invention relates to an electrode active material for lithium ion batteries, which contains granular porous silicon or silicon alloy, and sodium ions, wherein the sodium ions are intercalated into the granular porous silicon or silicon alloy.
  • the sodium ions can be present in a form of sodium-silicon alloy. As illustrated in Fig. 3, the sodium ions are not extracted from the anode material any more at the end of the formation process and during the subsequent cycling processes, but retained in the granular porous silicon or silicon alloy to form a sodium-silicon alloy. Since the radius of sodium ions is bigger than that of lithium ions, the sodium ions can act as pillars in the silicon structure during cycling, so as to diminish volume shrinking during cycling and keep the channels for lithiation/delithiation open. On the other hand, lithium ions can be extracted from and intercalated into the sodium source material, in addition to the cathode active material, during the subsequent cycling processes, wherein the sodium ions of the sodium source material have been partially replaced with lithium ions.
  • the content of the sodium ions can be 0.1 –5 wt. %, preferably 0.5 –2 wt. %, more preferably 0.8 –1.5 wt. %, based on the weight of the electrode active material.
  • the average diameter of the granular porous silicon or silicon alloy can be 20 nm –20 ⁇ m, preferably 0.1 –10 ⁇ m.
  • the BET specific surface area of the granular porous silicon or silicon alloy can be 5 –500 m 2 /g.
  • the pore volume of the granular porous silicon or silicon alloy can be 0.3 – 50.0 cm 3 /g.
  • the average pore diameter of the granular porous silicon or silicon alloy can be 0.2 nm –0.1 ⁇ m.
  • the present invention relates to an anode, which contains the electrode active material according to the present invention.
  • the present invention relates to a lithium-ion battery, which contains the anode according to the present invention.
  • the present invention relates to a method for preparing a lithium-ion battery, said method including the following steps:
  • a cathode active material together with one or more sodium source materials can be provided, and granular porous silicon or silicon alloy can be provided as the anode active material.
  • the sodium source materials can be one or more selected from the cathode active materials usable in sodium ion batteries.
  • the sodium source materials can be one or more selected from the group consisting of
  • said one or more transition metals can be selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc.
  • the sodium source materials can be one or more selected from the group consisting of sodium vanadium phosphate, sodium iron phosphate, sodium vanadium fluorophosphate, sodium iron fluorophosphate, and sodium ferrocyanide.
  • the sodium source material can be dehydrated.
  • the weight proportion of the cathode active material to the sodium source material can be 12.6 : 1 –9 : 1, preferably 11.6 : 1 –10 : 1, more preferably 11.1: 1 –10.5 : 1.
  • step 2) the cathode active material together with one or more sodium source materials of step 1) , the anode active material of step 1) , a separator, and an electrolyte such as 1M LiPF 6 in EC: DMC (1: 1 in molar ratio) can be assembled to obtain a lithium-ion battery.
  • an electrolyte such as 1M LiPF 6 in EC: DMC (1: 1 in molar ratio
  • the cathode active material together with one or more sodium source materials of step 1) can be mixed with carbon black, graphite and a binder such as poly- (vinyl difluoride) (PVDF) in a solvent such as DMF, TMF, THF, or NMP, and pasted onto an aluminium foil, and dried.
  • a binder such as poly- (vinyl difluoride) (PVDF) in a solvent such as DMF, TMF, THF, or NMP
  • the anode active material of step 1) can be mixed with carbon black, graphite and a binder such as sodium polyacrylate, and pasted onto a copper foil, and dried.
  • step 3) the lithium-ion battery of step 2) can be subjected to a formation process.
  • the formation process can be carried out at a current density of C/5 –C/100, preferably C/10 –C/50, more preferably about C/20.
  • the lithium-ion battery of step 2) can be charged to 3.7 –4.0 V, preferably 3.8 –3.9 V, more preferably about 3.85 V, held for 1 –10 hours, preferably 4 –6 hours, and then further charged to the charge cutoff voltage.
  • the formation process can be carried out to a charge cutoff voltage of 4.15 –4.25 V, preferably about 4.2 V, and to a discharge cutoff voltage of 2.4 –2.6 V, preferably about 2.5 V.
  • the formation process can be carried out to a charge cutoff voltage of 4.3 –4.4 V, preferably about 4.35 V, and to a discharge cutoff voltage of 2.9 –3.1 V, preferably about 3.0 V.
  • sodium ions can be extracted from the cathode into the electrolyte (see Fig. 1) , and intercalated from the electrolyte into the anode (see Fig. 2) .
  • sodium ions can be intercalated into the granular porous silicon or silicon alloy of the anode active material to form a sodium-silicon alloy.
  • the sodium ions are not extracted from the anode material any more at the end of the formation process and during the subsequent cycling processes, but retained in the granular porous silicon or silicon alloy to form a sodium-silicon alloy. Since the radius of sodium ions is bigger than that of lithium ions, the sodium ions can act as pillars in the silicon structure during cycling, so as to diminish volume shrinking during cycling and keep the channels for lithiation/delithiation open.
  • lithium ions can be extracted from and intercalated into the sodium source material, in addition to the cathode active material, during the subsequent cycling processes, wherein the sodium ions of the sodium source material have been partially replaced with lithium ions.
  • said method can optionally further include a step 4) after step 3) , in which step 4) the electrolyte can be replaced with fresh electrolyte having the same composition such as 1 M LiPF 6 in EC: DMC (1: 1 in molar ratio) , so that the electrolyte in the battery essentially does not contain sodium ions any more, as illustrated in Fig. 3.
  • sodium can be used to activate the silicon anode.
  • the sodium source materials can be initially incorporated into the cathode.
  • sodium ions can be extracted from the cathode structure, and diffuse from the cathode side to the anode side. And then, lithium and sodium ions in the electrolyte can be intercalated into the silicon anode.
  • the sodium ions can act as pillars in the silicon structure, so as to diminish the volume change during the charging and discharging processes. Thus, a better cycling performance and a better rate capability can be achieved.
  • the volume of the silicon structure will expand, but not shrink, so that the volume change can be diminished
  • the diffusion channel for lithium ions can be expanded, so as to enhance the Li + conductivity
  • volume change results in loss of electrical contact between silicon particles, while according to the present invention, the volume change can be diminished, and a better electronic conductivity can be achieved.
  • Na 4 Fe (CN) 6 ⁇ xH 2 O was used as the sodium source material, and dehydrated overnight to obtain Na 4 Fe (CN) 6 . Then Na 4 Fe (CN) 6 was mixed with conductive carbon black Super P (commercially available from Timcal) in a weight ratio of 8 : 2 by a ball mill machine at a speed of 200 rpm for 2 hours to obtain a preliminary mixture.
  • conductive carbon black Super P commercially available from Timcal
  • the intermediate mixture was added to NMP solvent to obtain a cathode slurry, wherein the solid content of the cathode slurry was adjusted to about 68 wt. %.
  • the cathode slurry was pasted onto an aluminium foil, and dried at about 80°C, so as to obtain the cathode.
  • anode composition 40 wt. %of granular porous silicon alloy (commercially available from 3M) , 40 wt. %of graphite (commercially available from BTR) , 10 wt. %of sodium polyacrylate (NaPAA) , 8 wt.%of flake graphite (commercially available from Timcal) and 2 wt. %of conductive carbon black Super P (commercially available from Timcal) were used to prepare an anode composition. The anode composition was pasted onto a copper foil, and dried, so as to obtain the anode.
  • the cathode, the anode, the electrolyte, and the separator were assembled in an argon-filled glove box (MB-10 compact, MBraun) to obtain a pouch cell.
  • the electrochemical performance was evaluated on a LAND-CT 2001A Battery test system (Wuhan, China) at room temperature.
  • the pouch cell was subjected to a formation process, in which the pouch cell was charged to 3.85 V at a current density of C/20, held for 5 hours, further charged to 4.2 V, and discharged to 2.5 V. During the subsequent cycling processes the pouch cell was charged to 4.2 V and discharged to 2.5 V at a current density of 0.5C.
  • Fig. 4 shows the cycling performances of the lithium-ion battery of Example 1 (E1) .
  • Example 2 (E2) was carried out similar to Example 1, except that during the subsequent cycling processes the pouch cell was charged and discharged at a current density of 0.1C every 50 cycles and at a current density of 0.5C for other cycles.
  • Fig. 4 shows the cycling performances of the lithium-ion battery of Example 2 (E2) .
  • Example 3 (E3) was carried out similar to Example 1, except that during the formation process the pouch cell was charged to 3.85 V at a current density of C/20, held for 5 hours, further charged to 4.35 V, and discharged to 3 V; and that during the subsequent cycling processes the pouch cell was charged to 4.35 V and discharged to 3 V at a current density of 0.1C every 50 cycles and at a current density of 0.5C for other cycles.
  • Fig. 4 shows the cycling performances of the lithium-ion battery of Example 3 (E3) .
  • Comparative Example (CE) was carried out similar to Example 1, except that the cathode was prepared without sodium source material.
  • Fig. 4 shows the cycling performances of the lithium-ion battery of Comparative Example (CE) .
  • Electrodes active material include, but are not limited to, high-energy-density lithium ion batteries with acceptable high power density for energy storage applications, such as power tools, photovoltaic cells and electric vehicles.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne un matériau actif d'électrode destiné à des batteries au lithium-ion, qui contient du silicium poreux granulaire ou un alliage de silicium et des ions sodium, les ions sodium étant intercalés dans le silicium poreux granulaire ou dans l'alliage de silicium. La présente invention concerne également une anode, contenant ledit matériau actif d'électrode et une batterie au lithium-ion, contenant ladite anode. La présente invention concerne également un procédé de fabrication d'une batterie au lithium-ion.
PCT/CN2017/078550 2017-03-29 2017-03-29 Matériau actif d'électrode, anode et batterie contenant ledit matériau actif d'électrode et procédé de fabrication d'une batterie Ceased WO2018176254A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201780089129.6A CN110462890B (zh) 2017-03-29 2017-03-29 电极活性材料、包含所述电极活性材料的负极和电池以及制备所述电池的方法
PCT/CN2017/078550 WO2018176254A1 (fr) 2017-03-29 2017-03-29 Matériau actif d'électrode, anode et batterie contenant ledit matériau actif d'électrode et procédé de fabrication d'une batterie

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PCT/CN2017/078550 WO2018176254A1 (fr) 2017-03-29 2017-03-29 Matériau actif d'électrode, anode et batterie contenant ledit matériau actif d'électrode et procédé de fabrication d'une batterie

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Cited By (1)

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CN117886297A (zh) * 2024-01-19 2024-04-16 厦门兴荣锂源科技有限公司 一种使用废旧电池修复再生制备的氟磷酸铁钠正极材料

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CN114551880B (zh) * 2021-12-21 2023-07-14 杭州华宏通信设备有限公司 一种碳覆多孔Cr-Cu合金/磷酸铁锂正极及其制备方法

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CN103247792A (zh) * 2013-03-22 2013-08-14 济南大学 一类纳米多孔硅合金材料及其制备方法

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CN102810669A (zh) * 2011-05-31 2012-12-05 现代自动车株式会社 二次电池用正极材料和制造该材料的方法
CN103247792A (zh) * 2013-03-22 2013-08-14 济南大学 一类纳米多孔硅合金材料及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117886297A (zh) * 2024-01-19 2024-04-16 厦门兴荣锂源科技有限公司 一种使用废旧电池修复再生制备的氟磷酸铁钠正极材料

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CN110462890B (zh) 2022-08-16

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