WO2022194089A1 - 负极材料及其制备方法和全固态锂电池 - Google Patents

负极材料及其制备方法和全固态锂电池 Download PDF

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WO2022194089A1
WO2022194089A1 PCT/CN2022/080644 CN2022080644W WO2022194089A1 WO 2022194089 A1 WO2022194089 A1 WO 2022194089A1 CN 2022080644 W CN2022080644 W CN 2022080644W WO 2022194089 A1 WO2022194089 A1 WO 2022194089A1
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negative electrode
electrode material
amorphous
solid electrolyte
silicon alloy
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PCT/CN2022/080644
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English (en)
French (fr)
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历彪
郭姿珠
张桐
时琢
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比亚迪股份有限公司
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Priority to KR1020237031366A priority Critical patent/KR20230145437A/ko
Priority to JP2023556970A priority patent/JP2024510485A/ja
Priority to EP22770444.2A priority patent/EP4293750A1/en
Publication of WO2022194089A1 publication Critical patent/WO2022194089A1/zh
Priority to US18/463,954 priority patent/US20230420663A1/en

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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
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Definitions

  • the present application relates to the technical field of batteries, in particular to negative electrode materials and preparation methods thereof, and all-solid-state lithium batteries.
  • the present application provides a negative electrode material, a preparation method thereof, and an all-solid-state lithium battery, which have good contact between the negative electrode materials, small volume expansion effect of the negative electrode material in the process of removing/intercalating lithium, and good cycle stability. , the electrochemical performance is excellent, so the all-solid-state lithium battery prepared by using the negative electrode material has the advantages of high capacity and good cycle performance, which is beneficial to its application.
  • the present application provides a negative electrode material
  • the negative electrode material includes an inner core and an amorphous lithium-silicon alloy layer covering the inner core
  • the inner core includes a glassy solid electrolyte and dispersed in the glassy solid Amorphous lithium-silicon alloy particles in the electrolyte
  • the material of the amorphous lithium-silicon alloy particles is Li x Si, 0 ⁇ x ⁇ 4.4
  • the material of the amorphous lithium-silicon alloy layer is Li y Si, 0 ⁇ y ⁇ 4.4.
  • the mass ratio of the amorphous lithium-silicon alloy particles to the amorphous lithium-silicon alloy layer is (1-100):1.
  • the mass fraction of the amorphous lithium-silicon alloy particles is 50%-95%.
  • the particle size of the amorphous lithium-silicon alloy particles is 10 nm-1 ⁇ m.
  • the thickness of the amorphous lithium-silicon alloy layer is 5 nm-1 ⁇ m.
  • the particle size of the negative electrode material is 20 nm-20 ⁇ m.
  • the glassy solid electrolyte includes at least one of a glassy oxide solid electrolyte and a glassy sulfide solid electrolyte.
  • the glassy solid electrolyte comprises: 30 mol%-80 mol% Li 2 S, 10 mol %-50 mol % P 2 S 5 , 0 mol %-30 mol % SiS in molar percentage 2 and 0-30 mol% LiA, wherein A is at least one of Cl, Br, and I.
  • the glassy solid electrolyte includes, in molar percentage, 30-80 mol% Li 2 O, 10-50 mol % P 2 O 5 , 0-30 mol % SiS 2 and 0-30 mol% LiA, wherein A is at least one of Cl, Br, and I.
  • the glassy solid electrolyte includes, in molar percentage, 30-80 mol% Li 2 O, 20-60 mol % B 2 O 3 and 0-30 mol % LiA , where A is at least one of Cl, Br and I.
  • the glassy solid electrolyte comprises, in molar percentage, 30 mol%-80 mol% Li 2 S, 20 mol %-60 mol % SiS 2 and 0 mol %-30 mol % LiA, wherein , A is at least one of Cl, Br and I.
  • the glassy solid electrolyte comprises: 30mol%-85mol% Li2O and 15mol%-70mol% LiA, wherein A is among Cl, Br and I at least one of.
  • the outermost layer is an amorphous lithium-silicon alloy layer, so that the contact performance between the negative electrode materials is good, which is beneficial to reduce impedance; and the amorphous lithium-silicon alloy particles are dispersed in the glassy state.
  • the solid electrolyte acts as the inner core, and the glassy solid electrolyte acts as the skeleton of the inner core to support and disperse the amorphous lithium-silicon alloy particles and buffer the volume expansion of the amorphous lithium-silicon alloy particles, thereby reducing the process of de/lithium intercalation of the negative electrode material.
  • the amorphous lithium-silicon alloy layer fixes the inner core to ensure adequate mixing and contact between the amorphous lithium-silicon alloy particles and the glassy solid electrolyte, and the anode materials are all amorphous lithium-silicon materials and
  • the glassy solid electrolyte is isotropic, which is beneficial to improve the transmission efficiency of lithium ions, thereby improving the electrochemical performance of the negative electrode material.
  • the application also provides a method for preparing a negative electrode material, comprising:
  • the inner core is coated with amorphous Li y Si to obtain a negative electrode material, wherein 0 ⁇ y ⁇ 4.4.
  • coating the inner core with amorphous Li y Si includes: ball-milling Li y Si to obtain the amorphous Li y Si; combining the inner core and the amorphous Li y Si The amorphous Li y Si coats the inner core after the mixed ball milling of the morphological Li y Si .
  • the method for preparing a negative electrode material provided in the second aspect of the present application can prepare the above-mentioned negative electrode material with good contact, small volume expansion effect in the process of de/lithium intercalation, good cycle stability and excellent electrochemical performance, and the process is simple, It is easy to operate, suitable for industrial production, and beneficial to the application of negative electrode materials.
  • the present application also provides an all-solid-state lithium battery, comprising a positive electrode, a negative electrode, and a solid-state electrolyte layer between the positive electrode and the negative electrode, the negative electrode comprising the negative electrode material described in the first aspect or the The negative electrode material prepared by the method described in the second aspect.
  • the negative electrode includes a negative electrode current collector and a negative electrode material layer disposed on the negative electrode current collector, and the negative electrode material layer includes the negative electrode material.
  • the negative electrode material layer does not contain a conductive agent.
  • the all-solid-state lithium battery provided by the third aspect of the present application has good cycle performance and excellent electrochemical performance, which is beneficial to its application.
  • FIG. 1 is a schematic structural diagram of a negative electrode material provided by an embodiment of the present application.
  • FIG. 2 is a schematic flowchart of a method for preparing a negative electrode material according to an embodiment of the present application.
  • FIG. 3 is a schematic structural diagram of an all-solid-state lithium battery provided by an embodiment of the present application.
  • FIG. 1 is a schematic structural diagram of a negative electrode material according to an embodiment of the application.
  • the negative electrode material includes an inner core 11 and an amorphous lithium-silicon alloy layer 12 covering the inner core 11 .
  • the inner core 11 includes a glassy solid electrolyte 111 and dispersed in The amorphous lithium-silicon alloy particles 112 in the glassy solid electrolyte 111, the material of the amorphous lithium-silicon alloy particles 112 is Li x Si, 0 ⁇ x ⁇ 4.4, and the material of the amorphous lithium-silicon alloy layer 12 is Li y Si, 0 ⁇ y ⁇ 4.4.
  • both amorphous lithium-silicon materials and glassy solid electrolytes used in the negative electrode material 10 are both amorphous and isotropic, so that lithium ions will not be affected by the insertion direction during de-intercalation. Therefore, it can be quickly deintercalated, which is conducive to the transport of lithium ions at the interface, improves the transport speed and distance of lithium ions, and improves the ionic conductivity; and, compared with crystalline materials, amorphous materials can be charged and discharged for a long time.
  • the internal structure change under the condition is small, the structure stability is good, and the service life is long.
  • the amorphous lithium-silicon alloy particles 112 in the negative electrode material 10 are dispersed in the glassy solid electrolyte 111 as the inner core 11, and the glassy solid electrolyte 111 is used as the skeleton of the inner core 11 to support and disperse the amorphous lithium-silicon alloy particles 112, which can effectively deal with
  • the volume of the amorphous lithium-silicon alloy particles 112 changes during the cycle, thereby reducing the volume expansion effect of the negative electrode material 10 during the process of lithium extraction/intercalation, and ensuring the structural stability of the negative electrode material 10 .
  • the outer shell of the negative electrode material 10 is an amorphous lithium-silicon alloy layer 12, so that when the negative electrode materials 10 are in contact, there will be no poor contact or high contact resistance due to differences in crystal phases and grain boundaries, and further It is beneficial to the contact between the negative electrode materials 10 and ensures the reduction of the interface impedance. Therefore, the negative electrode material 10 provided by the present application has good charge-discharge performance, good cycle performance and excellent electrochemical performance.
  • the glassy solid electrolyte 111 can effectively alleviate the volume expansion effect of the amorphous lithium-silicon alloy particles 112 and ensure the long-term stable use of the negative electrode material 10 .
  • the mass fraction of the amorphous lithium-silicon alloy particles 112 in the inner core 11 is 50%-95%. Further, the mass fraction of the amorphous lithium-silicon alloy particles 112 in the inner core 11 is 60%-90%. Furthermore, the mass fraction of the amorphous lithium-silicon alloy particles 112 in the inner core 11 is 70%-85%. Specifically, the mass fraction of the amorphous lithium-silicon alloy particles 112 in the inner core 11 may be, but not limited to, 55%, 57%, 60%, 65%, 72%, 75%, 78%, 80%, 83%, 86% % or 90% etc.
  • the shape of the amorphous lithium-silicon alloy particles 112 is not limited, and the shape of the amorphous lithium-silicon alloy particles 112 may be, but not limited to, spherical, quasi-spherical, and the like.
  • the particle size of the amorphous lithium-silicon alloy particles 112 is 10 nm-1 ⁇ m. It can be understood that when the material is spherical, the particle size is the equivalent particle size. Further, the particle size of the amorphous lithium-silicon alloy particles 112 is 150nm-950nm. Further, the particle size of the amorphous lithium-silicon alloy particles 112 is 230nm-870nm.
  • the particle size of the amorphous lithium-silicon alloy particles 112 may be, but not limited to, 10 nm, 80 nm, 150 nm, 200 nm, 300 nm, 500 nm, 650 nm, 700 nm, 820 nm, 900 nm, or 970 nm.
  • the mass fraction of the glassy solid electrolyte 111 in the inner core 11 is 5%-50%. Further, the mass fraction of the glassy solid electrolyte 111 in the inner core 11 is 10%-40%. Further, the mass fraction of the glassy solid electrolyte 111 in the inner core 11 is 15%-30%. Specifically, the mass fraction of the glassy solid electrolyte 111 in the inner core 11 may be, but not limited to, 10%, 14%, 17%, 20%, 22%, 25%, 28%, 35%, 40%, 43% or 45% %Wait.
  • the glassy solid electrolyte 111 By setting the glassy solid electrolyte 111 with the above content, the content of the amorphous lithium-silicon alloy in the inner core 11 is guaranteed, and it is beneficial to the intercalation and deintercalation of lithium ions, and the electrochemical performance of the negative electrode material 10 is improved.
  • the glassy solid electrolyte 111 includes at least one of a glassy oxide solid electrolyte and a glassy sulfide solid electrolyte.
  • the transport of lithium ions is facilitated by providing the above-described glassy solid electrolyte 111 .
  • the glassy solid electrolyte 111 includes, on a molar percentage basis: 30-80 mol% Li 2 S, 10-50 mol % P 2 S 5 , 0-30 mol % SiS 2 and 0 mol % -30 mol% LiA, wherein A is at least one of Cl, Br and I.
  • the glassy solid electrolyte 111 may include, but is not limited to, 65 mol % Li 2 S, 20 mol % P 2 S 5 , 5 mol % SiS 2 and 10 mol % LiA.
  • the glassy solid electrolyte 111 includes, on a molar percentage basis: 30-80 mol% Li 2 O, 10-50 mol % P 2 O 5 , 0-30 mol % SiS 2 and 0 mol %-30 mol% LiA, wherein A is at least one of Cl, Br, and I.
  • the glassy solid electrolyte 111 may include, but is not limited to, 50 mol % Li 2 O, 35 mol % P 2 O 5 , 10 mol % SiS 2 and 5 mol % LiA.
  • the glassy solid electrolyte 111 includes, in molar percentage, 30-80 mol% Li 2 O, 20-60 mol % B 2 O 3 and 0-30 mol % LiA, wherein, A is at least one of Cl, Br and I.
  • the glassy solid electrolyte 111 may include, but is not limited to, 70 mol % Li 2 O, 25 mol % B 2 O 3 and 5 mol % LiA in molar percentage.
  • the glassy solid electrolyte 111 includes 30mol%-80mol% Li2S , 20mol%-60mol% SiS2 and 0mol%-30mol% LiA in molar percentage, wherein A is At least one of Cl, Br and I.
  • the glassy solid electrolyte 111 may include, but is not limited to, 55 mol % Li 2 S, 25 mol % SiS 2 and 20 mol % LiA in molar percentage.
  • the glassy solid electrolyte 111 includes 30 mol%-85 mol% Li 2 O and 15 mol%-70 mol% LiA in molar percentage, wherein A is at least one of Cl, Br and I kind.
  • the glassy solid electrolyte 111 may include, but is not limited to, 70 mol % Li 2 O and 30 mol % LiA in molar percentage.
  • the contact performance between the negative electrode materials 10 is improved, which is beneficial to reduce the impedance of the negative electrode material 10 .
  • the values of x and y may be the same or different.
  • x and y are independently selected from 1.71, 2.33, 3.25, 3.75 or 4.4 and the like.
  • the thickness of the amorphous lithium-silicon alloy layer 12 is 5 nm-1 ⁇ m. Further, the thickness of the amorphous lithium-silicon alloy layer 12 is 60 nm-950 nm. Further, the thickness of the amorphous lithium-silicon alloy layer 12 is 150nm-820nm. Specifically, the thickness of the amorphous lithium-silicon alloy layer 12 may be, but not limited to, 10 nm, 80 nm, 150 nm, 200 nm, 300 nm, 500 nm, 650 nm, 700 nm, 820 nm, 900 nm, or 970 nm.
  • the thickness of the amorphous lithium-silicon alloy layer 12 is relatively thin, and the amorphous lithium-silicon alloy layer 12 mainly plays a role in fixing and protecting the inner core 11, and also improves the negative electrode. Contact properties between materials 10 .
  • the ratio of the radius of the inner core 11 to the thickness of the amorphous lithium-silicon alloy layer 12 is 2-9. Further, the ratio of the radius of the inner core 11 to the thickness of the amorphous lithium-silicon alloy layer 12 is 3-8. Furthermore, the ratio of the radius of the inner core 11 to the thickness of the amorphous lithium-silicon alloy layer 12 is 4-7.5.
  • the ratio of the radius of the inner core 11 to the thickness of the amorphous lithium-silicon alloy layer 12 may be, but not limited to, 2, 2.5, 4, 4.5, 5, 5.8, 6, 6.5, 7, 7.2, or 8.5, etc., which is beneficial to The content of the inner core 11 is increased, the transport of lithium ions is enhanced, and the specific capacity of the negative electrode material 10 is increased.
  • the mass ratio of the amorphous lithium-silicon alloy particles 112 to the amorphous lithium-silicon alloy layer 12 is (1-100):1. Further, the mass ratio of the amorphous lithium-silicon alloy particles 112 to the amorphous lithium-silicon alloy layer 12 is (10-95):1. Further, the mass ratio of the amorphous lithium-silicon alloy particles 112 to the amorphous lithium-silicon alloy layer 12 is (20-80): 1, (25-80): 1, (30-70): 1, ( 25-70): 1 or (30-65): 1 etc.
  • the mass ratio of the amorphous lithium-silicon alloy particles 112 to the amorphous lithium-silicon alloy layer 12 may be, but not limited to, 15:1, 20:1, 25:1, 30:1, 40:1, and 45:1. 1, 50:1, 55:1, 60:1, 70:1, 80:1, 90:1 or 95:1, etc., so that the amorphous lithium-silicon alloy particles 112 mainly play the role of intercalation and deintercalation of lithium ions , the amorphous lithium-silicon alloy layer 12 protects and fixes the inner core 11, and is beneficial to the improvement of the lithium ion transmission effect.
  • the particle size of the negative electrode material 10 is 20 nm-20 ⁇ m. Further, the particle size of the negative electrode material 10 is 100 nm-19 ⁇ m. Further, the particle size of the negative electrode material 10 is 0.5 ⁇ m-18 ⁇ m, 1 ⁇ m-17 ⁇ m, 2 ⁇ m-16 ⁇ m, 3 ⁇ m-15 ⁇ m, 5 ⁇ m-13 ⁇ m or 7 ⁇ m-12 ⁇ m and the like. Specifically, the particle size of the negative electrode material 10 may be, but not limited to, 50 nm, 1.5 ⁇ m, 2.8 ⁇ m, 4.5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12.5 ⁇ m, 14 ⁇ m, 16 ⁇ m, or 18 ⁇ m.
  • the ionic conductivity of the negative electrode material 10 at room temperature is above 10 -7 S ⁇ cm -1 , and the room temperature is 15°C-30°C.
  • the electron conductivity of the negative electrode material 10 at room temperature is 10 -2 S ⁇ cm -1 or more, and the room temperature is 15°C-30°C.
  • FIG. 2 is a schematic flowchart of a method for preparing a negative electrode material provided by an embodiment of the application, including:
  • the amorphous raw materials can be directly provided for mixing, or the amorphous raw materials can be obtained by ball milling.
  • dispersing the amorphous Li x Si particles in the glassy solid electrolyte includes: uniformly mixing the amorphous Li x Si particles and the glassy solid electrolyte.
  • dispersing the amorphous Li x Si particles in the glassy solid electrolyte includes: mixing the Li x Si particles with the solid electrolyte, and mixing by ball milling to obtain the amorphous Li x Si particles and A glassy solid electrolyte, and amorphous Li x Si particles are dispersed in the glassy solid electrolyte.
  • the rotational speed of the ball-milling mixing is 150rpm-350rpm, and the treatment time is 1h-5h. Further, the rotating speed of the ball mill mixing is 200rpm-300rpm, and the processing time is 2h-4h.
  • Amorphous raw materials can be obtained by long-time high-speed ball milling, and the contact performance between glassy solid electrolytes and between glassy solid electrolytes and amorphous Li x Si is good, which is beneficial to reduce impedance and improve ionic conductivity. .
  • dispersing the amorphous Li x Si particles in the glassy solid electrolyte is further heat-treated.
  • the heat treatment includes raising the temperature to 250°C-400°C at a rate exceeding 10°C/min, and maintaining the temperature for 10min-60min. Specifically, it may be, but not limited to, the temperature is raised to 300°C at a rate exceeding 10°C/min, and the temperature is maintained for 30 minutes.
  • coating the inner core 11 with amorphous Li y Si includes: ball-milling Li y Si to obtain amorphous Li y Si, and then mixing the inner core 11 and amorphous Li y Si with ball-milling , the amorphous Li y Si coats the core 11 .
  • the ball milling method may be wet ball milling or dry ball milling.
  • the solvent in wet ball milling may include, but is not limited to, toluene, xylene, anisole, heptane, decane, ethyl acetate, ethyl propionate, butyl butyrate, N-methylpyrrolidone, acetone, etc.
  • the rotation speed of the ball mill is 50rpm-250rpm, and the time is 5min-30min. Further, the rotational speed of the ball mill is 150rpm-250rpm, and the time is 20min-30min.
  • the preparation of the negative electrode material 10 is performed under a protective gas.
  • the protective gas includes at least one of nitrogen, helium, and hydrogen.
  • the method for preparing the negative electrode material 10 provided by the present application can prepare the above-mentioned negative electrode material with good contact, small volume expansion effect in the process of delithiation/intercalation, good cycle stability and excellent electrochemical performance, and the process is simple and easy to operate. , which is suitable for industrial production and is beneficial to the application of negative electrode materials.
  • FIG. 3 is a schematic structural diagram of an all-solid-state lithium battery according to an embodiment of the present application.
  • the all-solid-state lithium battery includes a positive electrode 200 , a negative electrode 100 , and a solid electrolyte layer 300 located between the positive electrode 200 and the negative electrode 100 , and the negative electrode 100 includes the above-mentioned The negative electrode material 10 in any of the embodiments.
  • the negative electrode 100 includes a negative electrode current collector 102 , and a negative electrode material layer 101 disposed on the negative electrode current collector 102 , and the negative electrode material layer 101 includes the negative electrode material 10 .
  • the thickness of the negative electrode material layer 101 may be, but not limited to, 5 ⁇ m-50 ⁇ m.
  • the negative electrode material layer 101 does not contain a conductive agent.
  • the negative electrode material layer 101 can include the negative electrode material 10 having a large content and having electrochemical activity, thereby enabling the negative electrode 100 to have a larger capacity and a higher energy density of the all-solid-state lithium battery.
  • the negative electrode material layer 101 further includes at least one kind of binder.
  • the binder helps to firmly fix the negative electrode material layer 101 on the negative electrode current collector 102 and makes the negative electrode material layer 101 have certain elasticity.
  • the binder may include, but is not limited to, polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene- Diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl At least one of cellulose, polyethylene oxide, sodium carboxymethyl cellulose and styrene-butadiene rubber.
  • the mass percentage content of the binder in the negative electrode material layer 101 is 0.5%-5%.
  • the mass percentage content of the binder in the negative electrode material layer 101 may be, but not limited to, 1%-5%, 1.5%-4.5%, 2%-4%, or 2.5%-3.8%.
  • the positive electrode 200 may include a positive electrode current collector 202 and a positive electrode material layer 201 disposed on the positive electrode current collector 202 .
  • the positive electrode material layer 201 may include a positive electrode active material, a conductive agent, a solid electrolyte material for positive electrodes, and a binder for positive electrodes.
  • the positive electrode active material includes one or more of oxide type, sulfide type, polyanion type, and composites of the above materials.
  • the oxide-type positive electrode active material may include, but is not limited to, one or more of LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 .
  • the sulfide-type cathode active material may include, but is not limited to, TiS 2 , V 2 S 3 , FeS, FeS 2 , WS 2 , LiJS i (J is selected from Ti, Fe, Ni, Cu and At least one of Mo, at least one of 1 ⁇ i ⁇ 2.5) and the like.
  • the polyanionic positive active material may include, but is not limited to, at least one of LiFePO 4 , Li 3 V 2 (PO 4 ) 3 , Li 3 V 3 (PO 4 ) 3 and LiVPO 4 F kind.
  • the particle diameter of the positive electrode active material is 100 nm to 500 ⁇ m.
  • the particle size of the positive electrode active material may be, but not limited to, 100 nm-100 ⁇ m, 100 nm-50 ⁇ m, or 500 nm-50 ⁇ m, and the like.
  • the surface of the positive electrode active material may also be provided with a coating layer to optimize the interface between the positive electrode material layer 201 and the solid electrolyte, reduce the interface impedance, and improve the cycle stability.
  • the coating layer on the surface of the positive electrode active material may include, but is not limited to, LiNbO 3 , LiTaO 3 , Li 3 PO 4 , Li 4 Ti 5 O 12 , and the like.
  • the binder for the positive electrode in the positive electrode material layer 201 is not particularly limited.
  • it may include, but is not limited to, at least one of fluorine-containing resin, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, polyolefin, styrene-butadiene rubber, and the like.
  • the conductive agent in the positive electrode material layer 201 includes but is not limited to conductive carbon black (such as acetylene black, Ketjen black), carbon nanotubes, carbon fibers and graphite. at least one of them.
  • the mass percentage content of the positive electrode binder in the positive electrode material layer 201 is 0.01%-10%. Specifically, the mass percentage content of the positive electrode binder in the positive electrode material layer 201 may be, but not limited to, 0.015%-8%, 0.02%-7%, 0.02%-5%, or 0.05%-4.5%. In another embodiment of the present application, the mass percentage content of the conductive agent in the positive electrode material layer 201 is 0.1%-20%. Specifically, the mass percentage content of the conductive agent in the positive electrode material layer 201 may be, but not limited to, 0.5%-18%, 1%-15%, 1%-10%, or 3%-8.5%.
  • the negative electrode current collector 102 and the positive electrode current collector 202 are independently selected from metal foils or alloy foils.
  • metal foils include but are not limited to copper, titanium, aluminum, platinum, iridium, ruthenium, nickel, tungsten, tantalum, gold or silver foils
  • alloy foils include but are not limited to stainless steel, or copper, titanium, aluminum, Alloys of at least one element of platinum, iridium, ruthenium, nickel, tungsten, tantalum, gold and silver.
  • the negative electrode current collector 102 may be specifically an aluminum foil
  • the positive electrode current collector 202 may be specifically a copper foil.
  • the thickness and surface roughness of the negative electrode current collector 102 and the positive electrode current collector 202 can be adjusted according to actual needs.
  • the solid electrolyte layer 300 may be formed by coating and drying a slurry containing a solid electrolyte material and a solvent, and the composition of the solid electrolyte layer 300 includes the solid electrolyte material.
  • the solid electrolyte layer 300 may further contain a binder, and the material thereof may be selected from the binder in the above-mentioned positive electrode material layer 201 , which will not be repeated here.
  • the solid electrolyte layer 300 can be combined with the negative electrode material layer 101 by coating, and then the solid electrolyte layer 300 can be combined with the positive electrode 200 with the positive electrode material layer 201 by pressing.
  • the solid electrolyte material for the positive electrode and the solid electrolyte material in the solid electrolyte layer 300 are independently selected from sodium superion conductor (NASICON) solid electrolyte, garnet type solid electrolyte, perovskite type solid electrolyte and sulfur One or more of solid electrolytes.
  • the material of the solid electrolyte layer 300 is the same as or different from the solid electrolyte material for the positive electrode.
  • the composition of the solid electrolyte layer is selected from a reduction-resistant solid electrolyte material to protect the negative electrode material 10 of the negative electrode 100 and further improve the cycle stability of the negative electrode material 10 .
  • the particle size of the solid electrolyte material used may be 1 nm-5 ⁇ m.
  • the NASICON type solid electrolyte may include, but is not limited to, one or more of LiM 2 (PO 4 ) 3 and its dopants, wherein M is Ti, Zr, Ge, Sn or Pb,
  • the doping element used for the dopant is selected from one or more of Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta and V.
  • the chemical formula of the garnet-type solid electrolyte is Li 7+pq-3u Al u La 3-p X p Zr 2-q Y q O 12 , wherein 0 ⁇ p ⁇ 1, 0 ⁇ q ⁇ 1, 0 ⁇ u ⁇ 1, X is selected from at least one of La, Ca, Sr, Ba and K, and Y is selected from at least one of Ta, Nb, W and Hf.
  • Glassy Li 2 SP 2 S 5 includes different products composed of Li 2 S and P 2 S 5 , for example, including Li 7 P 3 S 11 or 70Li 2 S-30P 2 S 5 and the like.
  • a method for preparing an all-solid-state lithium battery including:
  • S201 preparing the negative electrode 100 : the negative electrode material 10 is mixed with the first solvent to obtain a negative electrode mixed slurry; the negative electrode mixed slurry is coated on the negative electrode current collector 102 , and is dried and pressed to obtain the negative electrode 100 .
  • S203 preparing the positive electrode 200: mixing the positive electrode active material, the solid electrolyte for the positive electrode, the conductive agent, the binder for the positive electrode and the third solvent uniformly to obtain a positive electrode mixed slurry; the positive electrode mixed slurry is coated on the positive electrode current collector 202, After drying and tableting, the positive electrode 200 was obtained.
  • the first solvent, the second solvent and the third solvent are independently selected from water, ethanol, toluene, xylene, anisole, acetonitrile, heptane, decane, ethyl acetate, ethyl propionate At least one of ester, butyl butyrate, N-methylpyrrolidone, acetone and the like.
  • the amount of each solvent can generally be 50wt%-400wt% of the dry material mass in the corresponding mixed slurry.
  • the pressed sheet may be subjected to rolling treatment at, but not limited to, 0-5 MPa.
  • the temperature of the hot-pressing treatment may be, but not limited to, about 100° C.
  • the hot-pressing treatment time may be, but not limited to, 0.5h-3h
  • the pressure of the isostatic pressing may be, but not limited to, 100MPa or more, for example The pressure is 100MPa-300MPa
  • the time of isostatic pressing can be but not limited to 3min-10min.
  • the all-solid-state lithium battery provided by the present application because the above-mentioned negative electrode material 10 is included, the all-solid-state lithium battery has high battery capacity and good cycle performance, which is beneficial to its application.
  • a method for preparing an all-solid-state lithium battery comprising the following steps:
  • Li 2 S Under an argon atmosphere, 31g of Li 2 S, 60g of P 2 S 5 , 7g of SiS 2 , 2g of P 2 O 5 , and 1000g of Li 2.3 Si were placed together in a ball mill jar, and an appropriate amount of ZrO 2 grinding beads were added. , high-energy ball milling at 200 rpm for 2 hours, then transferred to an electric furnace (under protective atmosphere), heated to 300 ° C at a heating rate of not less than 10 ° C/min, and held for 30 min to obtain an inner core, the inner core includes Li 2 S, P 2 A glassy solid electrolyte formed by S 5 , SiS 2 and P 2 O 5 , and amorphous Li 2.3 Si particles dispersed therein.
  • LiCoO 2 , 51mL niobium ethoxide, 12g lithium ethoxide, 1000mL deionized water and 1000mL ethanol were thoroughly mixed, and under continuous stirring, ammonia water was added dropwise to adjust the pH to 10, the solution was evaporated to dryness, and the obtained powder was heated at 400°C. After heating for 8 h, a LiCoO 2 positive active material coated with LiNbO 3 was obtained.
  • LiCoO2 positive active material covered by LiNbO3 150g Li10GeP2S12 solid electrolyte material, 30g binder butadiene rubber, 20g acetylene black, 20g carbon fiber were added to 1500g toluene solvent, Then stir in a vacuum mixer to form a stable and uniform positive mixed slurry; the positive mixed slurry is uniformly and intermittently coated on aluminum foil (width 160mm, thickness 16 ⁇ m), then dried at 393K, and pressed by a roller press After sheeting, a positive electrode material layer with a thickness of 100 ⁇ m was formed on the aluminum foil to obtain a positive electrode.
  • the above positive electrode and the negative electrode with solid electrolyte layer were aligned and placed in a tablet press, fit the tabs, hot-pressed at 100 °C for 1 h, vacuum-sealed with aluminum-plastic film, and finally placed in an isostatic Press in the press for 300s under 200MPa to obtain an all-solid-state lithium battery.
  • a method for preparing an all-solid-state lithium battery which is roughly the same as Example 1, except that Li 2.3 Si becomes Li 4.4 Si, Li 1.71 Si becomes Li 3.75 Si, and LiNbO 3 -coated LiCoO 2 positive active material becomes TiS 2 .
  • the particle samples were cut by focused ion beam ( FIB ) and observed by scanning electron microscope ( SEM ). The overall average particle size is about 1.3 ⁇ m.
  • a method for preparing an all-solid-state lithium battery which is roughly the same as Example 1 , except that 12.4g of Li2S , 24g of P2S5 , 2.8g of SiS2 , and 0.8g of P2O5 are used , 1000g of Li 2.3 Si were placed in a ball milling jar, an appropriate amount of ZrO 2 grinding beads were added, and the ball was milled at a high energy of 150 rpm for 0.3 h, and then transferred to an electric furnace (under a protective atmosphere). The heating rate was increased to 300° C. and held for 30 min to obtain the inner core, and the rest of the steps remained unchanged.
  • the particle samples were cut by focused ion beam ( FIB ) and observed by scanning electron microscope ( SEM ). The overall average particle size of the particles is about 30 ⁇ m.
  • a method for preparing an all-solid-state lithium battery which is different from Example 1 in that a carbon-coated silicon negative electrode material is used to replace the negative electrode material, wherein the carbon-coated silicon negative electrode material preparation method comprises: mixing 1000 g of Si and 240 g of The sucrose was placed in 1000 mL of deionized water and stirred evenly, and then heated to 100 ° C during the stirring process. After the water evaporated, the solid matter was taken out and heated to 300 ° C under an inert atmosphere to obtain a carbon-coated silicon anode material. The coated silicon anode material is directly used as the anode, and the rest of the steps remain unchanged.
  • a method for preparing an all-solid-state lithium battery which is different from Example 1 in that the specific operation of step (1) is as follows: 1000 g of Si and 240 g of sucrose are placed in 1000 mL of deionized water and stirred evenly, and then stirred In the process of heating to 100 ° C, after the water evaporates, the solid material is taken out, and heated to 300 ° C under an inert atmosphere to obtain a carbon-coated silicon anode material; 1000 g of carbon-coated silicon anode material is mixed with 150 g of 70Li 2 S ⁇ 30P 2 S 5 glassy electrolyte material, 100 g of acetylene black and 1500 mL of toluene were prepared into a mixed slurry, which was coated on copper foil, dried and pressed to obtain a negative electrode, and the remaining steps remained unchanged.
  • a method for preparing an all-solid-state lithium battery which is different from Example 1 in that 1000 g of the inner core and 50 g of amorphous Li 1.71 Si in step (1) are directly mixed with 30 g of binder SBR rubber, 1500 mL of toluene The solution was mixed as a negative electrode slurry, and 950 g of the inner core and 50 g of amorphous Li 1.71 Si were not coated, and the rest of the steps remained unchanged.
  • a method for preparing an all-solid-state lithium battery which is different from Example 1 in that in step (1), 310 g of Li 2 S, 600 g of P 2 S 5 , 70 g of SiS 2 , and 20 g of P 2 O 5 They were placed together in a ball-milling jar, added an appropriate amount of ZrO 2 grinding beads, milled with high energy at 200 rpm for 2 hours, and then transferred to an electric heating furnace. state solid electrolyte; 90g glassy solid electrolyte, 910g Li 2.3 Si and 50g Li 1.71 Si were directly mixed with 30g binder SBR rubber and 1500mL toluene solution as negative electrode slurry, and the rest of the steps remained unchanged.
  • a method for preparing an all-solid-state lithium battery, which is different from Example 1 is that after obtaining the inner core in step (1), it is directly used to coat the negative electrode sheet, and the coating of the outer shell amorphous Li 1.71 Si is not carried out, The rest of the steps remain unchanged.
  • the battery cycle life test was carried out on the all-solid-state lithium batteries obtained in the above-mentioned Examples 1-3 and Comparative Examples 1-5, and the test method was as follows: 20 all-solid-state lithium battery samples obtained in each embodiment and Comparative Example were taken. , On the LAND CT 2001C secondary battery performance testing device, under the condition of 298 ⁇ 1K, each battery was charged and discharged at a rate of 0.1C for a charge-discharge cycle test.
  • test steps are as follows: set aside for 10min; charge with constant voltage to 4.25V/0.05C cut-off; set aside for 10min; discharge with constant current to 3V, which is 1 cycle, record the discharge capacity of the first cycle (using TiS 2 as the positive electrode, the upper and lower voltage limits 3V/0.05C and 1V respectively, other conditions are the same).
  • the battery capacity is lower than 80% of the initial discharge capacity during the cycle, the cycle is terminated.
  • the number of cycles at the end of the cycle is the cycle life of the battery.
  • the average value of each group is obtained. The results are shown in Table 1. Show.

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Abstract

本申请提供了一种负极材料及其制备方法和全固态锂电池，所述负极材料包括内核以及包覆所述内核的无定形态锂硅合金层，所述内核包括玻璃态固体电解质以及分散在所述玻璃态固体电解质中的无定形态锂硅合金颗粒，所述无定形态锂硅合金颗粒的材质为Li xSi，0＜x≤4.4，所述无定形态锂硅合金层的材质为Li ySi，0＜y≤4.4。

Description

负极材料及其制备方法和全固态锂电池
优先权信息
本申请请求于2021年03月19日向中国国家知识产权局提交的、专利申请号为202110305372.5、申请名称为“负极材料及其制备方法和全固态锂电池”的中国专利申请的优先权，并且其全部内容通过引用结合在本公开中。
技术领域
本申请涉及电池技术领域，具体涉及负极材料及其制备方法和全固态锂电池。
背景技术
近年来，使用固态电解质的全固态锂电池因具有较高的安全性而得到广泛关注。其中，理论比容量较高、安全性高的硅负极被认为是突破全固态锂电池能量密度的有效路径。然而，现有的硅负极材料在脱/嵌锂的过程中易发生巨大的体积变化，从而导致全固态锂电池的容量迅速衰减，循环性能变差，并且硅负极材料之间的接触性不佳，不利于阻抗的降低，限制了全固态锂电池的应用。
公开内容
有鉴于此，本申请提供一种负极材料及其制备方法和全固态锂电池，该负极材料之间的接触性好，负极材料在脱/嵌锂的过程中体积膨胀效应小，循环稳定性好，电化学性能优异，从而采用该负极材料制得的全固态锂电池具有容量高和循环性能好的优势，有利于其应用。
第一方面，本申请提供了一种负极材料，所述负极材料包括内核以及包覆所述内核的无定形态锂硅合金层，所述内核包括玻璃态固体电解质以及分散在所述玻璃态固体电解质中的无定形态锂硅合金颗粒，所述无定形态锂硅合金颗粒的材质为Li xSi，0＜x≤4.4，所述无定形态锂硅合金层的材质为Li ySi，0＜y≤4.4。
在本申请的一些实施例中，所述无定形态锂硅合金颗粒与所述无定形态锂硅合金层的质量比为(1-100)：1。
在本申请的一些实施例中，在所述内核中，所述无定形态锂硅合金颗粒的质量分数为50％-95％。
在本申请的一些实施例中，所述无定形态锂硅合金颗粒的粒径为10nm-1μm。
在本申请的一些实施例中，所述无定形态锂硅合金层的厚度为5nm-1μm。
在本申请的一些实施例中，所述负极材料的粒径为20nm-20μm。
在本申请的一些实施例中，所述玻璃态固体电解质包括玻璃态氧化物固体电解质和玻璃态硫化物固体电解质中的至少一种。
在本申请的一些实施例中，按摩尔百分比计，所述玻璃态固体电解质包括：30mol％-80mol％的Li 2S、10mol％-50mol％的P 2S 5、0mol％-30mol％的SiS 2和0mol％-30mol％的LiA，其中，A为Cl、Br和I中的至少一种。
在本申请的一些实施例中，按摩尔百分比计，所述玻璃态固体电解质包括：30mol％-80mol％的Li 2O、10mol％-50mol％的P 2O 5、0mol％-30mol％的SiS 2和0mol％-30mol％的LiA，其中，A为Cl、Br和I中的至少一种。
在本申请的一些实施例中，按摩尔百分比计，所述玻璃态固体电解质包括：30mol％-80mol％的Li 2O、20mol％-60mol％的B 2O 3和0mol％-30mol％的LiA，其中，A为Cl、Br和I中的至少一种。
在本申请的一些实施例中，按摩尔百分比计，所述玻璃态固体电解质包括：30mol％-80mol％的Li 2S、20mol％-60mol％的SiS 2和0mol％-30mol％的LiA，其中，A为Cl、Br和I中的至少一种。
在本申请的一些实施例中，按摩尔百分比计，所述玻璃态固体电解质包括：30mol％-85mol％的Li 2O和15mol％-70mol％的LiA，其中，A为Cl、Br和I中的至少一种。
本申请第一方面提供的负极材料中，最外层为无定形态锂硅合金层，使得负极材料之间的接触性能佳，有利于降低阻抗；并且无定形态锂硅合金颗粒分散在玻璃态固体电解质中作为内核，玻璃态固体电解质作为内核的骨架，支撑并分散无定形态锂硅合金颗粒，缓冲无定形态锂硅合金颗粒的体积膨胀，从而降低负极材料在脱/嵌锂的过程中体积膨胀效应；同时无定形态锂硅合金层固定内核，保证无定形态锂硅合金颗粒和玻璃态固体电解质的充分混合和接触，且负极材料中采用的均为无定形态的锂硅材料以及玻璃态的固体电解质，具有各向同性，有利于提升锂离子的传输效率，进而提高负极材料的电化学性能。
第二方面，本申请还提供了一种制备负极材料的方法，包括：
将无定形态Li xSi颗粒分散在玻璃态固体电解质中，得到内核，其中，0＜x≤4.4；
将所述内核用无定形态Li ySi包覆，得到负极材料，其中，0＜y≤4.4。
在本申请的一些实施例中，将所述内核用无定形态Li ySi包覆包括：将Li ySi进行球磨，得到所述无定形态Li ySi；将所述内核和所述无定形态Li ySi混合球磨后，所述无定形态Li ySi包覆所述内核。
本申请第二方面提供的制备负极材料的方法可以制备得到上述接触性好、在脱/嵌锂的过程中体积膨胀效应小、循环稳定性好以及电化学性能优异的负极材料，并且工艺简单， 易于操作，适用于工业化生产，有利于负极材料的应用。
第三方面，本申请还提供了一种全固态锂电池，包括正极、负极以及位于所述正极和负极之间的固态电解质层，所述负极包括如第一方面所述的负极材料或如采用第二方面所述的方法制备得到的负极材料。
在本申请的一些实施例中，所述负极包括负极集流体以及设置在所述负极集流体上的负极材料层，所述负极材料层包括所述负极材料。
在本申请的一些实施例中，所述负极材料层不含导电剂。
本申请第三方面提供的全固态锂电池的循环性能好，电化学性能优异，有利于其应用。
本公开的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本公开的实践了解到。
附图说明
此处所说明的附图用来提供对本申请的进一步理解，构成本申请的一部分，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：
图1为本申请一实施方式提供的负极材料的结构示意图。
图2为本申请一实施方式提供的制备负极材料的方法流程示意图。
图3为本申请一实施方式提供的全固态锂电池的结构示意图。
标号说明：
内核-11，玻璃态固体电解质-111，无定形态锂硅合金颗粒-112，无定形态锂硅合金层-12，负极材料-10，负极材料层-101，负极集流体-102，负极-100，正极材料层-201，正极集流体-202，正极-200，固态电解质层-300。
具体实施方式
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的保护范围。
下文的公开提供了许多不同的实施方式或例子用来实现本申请的不同结构。为了简化本申请的公开，下文中对特定例子的部件和设置进行描述。当然，它们仅仅为示例，并且目的不在于限制本申请。此外，本申请提供了的各种特定的工艺和材料的例子，但是本领域普通技术人员可以意识到其他工艺的应用和/或其他材料的使用。
请参阅图1，为本申请一实施方式提供的负极材料的结构示意图，负极材料包括内核11以及包覆内核11的无定形态锂硅合金层12，内核11包括玻璃态固体电解质111以及分散在玻璃态固体电解质111中的无定形态锂硅合金颗粒112，无定形态锂硅合金颗粒112的材质为 Li xSi，0＜x≤4.4，无定形态锂硅合金层12的材质为Li ySi，0＜y≤4.4。
在本申请中，负极材料10中采用的均为无定形态的锂硅材料以及玻璃态的固体电解质，均为非晶态，具有各向同性，使得锂离子脱嵌时不会受到嵌入方向的影响，从而可以快速脱嵌，有利于锂离子在界面处的传输，提升锂离子的传输速度和传输距离，提高离子电导率；并且，相比于晶态物质，非晶态物质在长期充放电条件下的内部结构变化小，结构稳定性佳，使用寿命长。负极材料10中无定形态锂硅合金颗粒112分散在玻璃态固体电解质111中作为内核11，玻璃态固体电解质111作为内核11的骨架，支撑并分散无定形态锂硅合金颗粒112，可以有效应对无定形态锂硅合金颗粒112在循环过程中的体积变化，从而降低负极材料10在脱/嵌锂的过程中体积膨胀效应，保证负极材料10结构稳定性。负极材料10的外壳为无定形态锂硅合金层12，从而使得负极材料10之间在接触时，不会存在因晶相和晶界的不同而产生接触不良或接触阻抗较大的情况，进而有利于负极材料10之间的接触，保证界面阻抗的降低。因此，本申请提供的负极材料10充放电性能佳，循环性能好，电化学性能优异。
在本申请中，玻璃态固体电解质111可以有效缓解无定形态锂硅合金颗粒112的体积膨胀效应，保证负极材料10长期稳定的使用。
在本申请实施方式中，内核11中无定形态锂硅合金颗粒112的质量分数为50％-95％。进一步的，内核11中无定形态锂硅合金颗粒112的质量分数为60％-90％。更进一步的，内核11中无定形态锂硅合金颗粒112的质量分数为70％-85％。具体的，内核11中无定形态锂硅合金颗粒112的质量分数可以为但不限于55％、57％、60％、65％、72％、75％、78％、80％、83％、86％或90％等。通过设置上述含量的无定形态锂硅合金颗粒112，保证了负极材料10的比容量，有利于其在全固态锂电池中的应用。
在本申请中，对无定形态锂硅合金颗粒112的形状不作限定，具体的可以为但不限于球形、类球形等。在本申请实施方式中，无定形态锂硅合金颗粒112的粒径为10nm-1μm。可以理解的，当材料为类球形，粒径为等效粒径。进一步的，无定形态锂硅合金颗粒112的粒径为150nm-950nm。更进一步的，无定形态锂硅合金颗粒112的粒径为230nm-870nm。具体的，无定形态锂硅合金颗粒112的粒径可以为但不限于10nm、80nm、150nm、200nm、300nm、500nm、650nm、700nm、820nm、900nm或970nm等。通过设置上述粒径的无定形态锂硅合金颗粒112，可以缓解负极材料10在脱/嵌锂的过程中体积膨胀效应，并提高锂离子脱嵌的电化学活性。
在本申请实施方式中，内核11中玻璃态固体电解质111的质量分数为5％-50％。进一步的，内核11中玻璃态固体电解质111的质量分数为10％-40％。更进一步的，内核11中玻璃态固体电解质111的质量分数为15％-30％。具体的，内核11中玻璃态固体电解质111的质量分数可以 为但不限于10％、14％、17％、20％、22％、25％、28％、35％、40％、43％或45％等。通过设置上述含量的玻璃态固体电解质111，保证了内核11中无定形态锂硅合金的含量，并且有利于锂离子的嵌脱，提高负极材料10的电化学性能。
在本申请实施方式中，玻璃态固体电解质111包括玻璃态氧化物固体电解质和玻璃态硫化物固体电解质中的至少一种。通过设置上述的玻璃态固体电解质111有利于锂离子的传输。在一实施例中，按摩尔百分比计，玻璃态固体电解质111包括：30mol％-80mol％的Li 2S、10mol％-50mol％的P 2S 5、0mol％-30mol％的SiS 2和0mol％-30mol％的LiA，其中，A为Cl、Br和I中的至少一种。具体的，按摩尔百分比计，玻璃态固体电解质111可以包括但不限于65mol％的Li 2S、20mol％的P 2S 5、5mol％的SiS 2和10mol％的LiA。在另一实施例中，按摩尔百分比计，玻璃态固体电解质111包括：30mol％-80mol％的Li 2O、10mol％-50mol％的P 2O 5、0mol％-30mol％的SiS 2和0mol％-30mol％的LiA，其中，A为Cl、Br和I中的至少一种。具体的，按摩尔百分比计，玻璃态固体电解质111可以包括但不限于50mol％的Li 2O、35mol％的P 2O 5、10mol％的SiS 2和5mol％的LiA。在另一实施例中，按摩尔百分比计，玻璃态固体电解质111包括：30mol％-80mol％的Li 2O、20mol％-60mol％的B 2O 3和0mol％-30mol％的LiA，其中，A为Cl、Br和I中的至少一种。具体的，按摩尔百分比计，玻璃态固体电解质111可以包括但不限于70mol％的Li 2O、25mol％的B 2O 3和5mol％的LiA。在另一实施例中，按摩尔百分比计，玻璃态固体电解质111包括：30mol％-80mol％的Li 2S、20mol％-60mol％的SiS 2和0mol％-30mol％的LiA，其中，A为Cl、Br和I中的至少一种。具体的，按摩尔百分比计，玻璃态固体电解质111可以包括但不限于55mol％的Li 2S、25mol％的SiS 2和20mol％的LiA。在另一实施例中，按摩尔百分比计，玻璃态固体电解质111包括：30mol％-85mol％的Li 2O和15mol％-70mol％的LiA，其中，A为Cl、Br和I中的至少一种。具体的，按摩尔百分比计，玻璃态固体电解质111可以包括但不限于70mol％的Li 2O和30mol％的LiA。
在本申请中，通过设置无定形态锂硅合金层12，提高负极材料10之间的接触性能，有利于降低负极材料10阻抗。其中，无定形态锂硅合金颗粒112的材质(Li xSi)与无定形态锂硅合金层12的材质(Li ySi)中，x与y取值可以相同也可以不同。在本申请一实施例中，2＜x≤4.4，2＜y≤4.4。具体的，x与y独立地选自1.71、2.33、3.25、3.75或4.4等。
在本申请实施方式中，无定形态锂硅合金层12的厚度为5nm-1μm。进一步的，无定形态锂硅合金层12的厚度为60nm-950nm。更进一步的，无定形态锂硅合金层12的厚度为150nm-820nm。具体的，无定形态锂硅合金层12的厚度可以为但不限于10nm、80nm、150nm、200nm、300nm、500nm、650nm、700nm、820nm、900nm或970nm等。通过设置上述厚度的无定形态锂硅合金层12，无定形态锂硅合金层12厚度相对较薄，无定形态锂硅合金层12主要对内核11起到固定和保护作用，还提高了负极材料10之间的接触性能。
在本申请实施方式中，内核11的半径与无定形态锂硅合金层12的厚度比值为2-9。进一步的，内核11的半径与无定形态锂硅合金层12的厚度比值为3-8。更进一步的，内核11的半径与无定形态锂硅合金层12的厚度比值为4-7.5。具体的，内核11的半径与无定形态锂硅合金层12的厚度比值可以为但不限于2、2.5、4、4.5、5、5.8、6、6.5、7、7.2或8.5等，从而有利于提高内核11含量，增强锂离子的传输，并提高负极材料10的比容量。
在本申请实施方式中，无定形态锂硅合金颗粒112与无定形态锂硅合金层12的质量比为(1-100)：1。进一步的，无定形态锂硅合金颗粒112与无定形态锂硅合金层12的质量比为(10-95)：1。更进一步的，无定形态锂硅合金颗粒112与无定形态锂硅合金层12的质量比为(20-80)：1、(25-80)：1、(30-70)：1、(25-70)：1或(30-65)：1等。具体的，无定形态锂硅合金颗粒112与无定形态锂硅合金层12的质量比可以为但不限于15：1、20：1、25：1、30：1、40：1、45：1、50：1、55：1、60：1、70：1、80：1、90：1或95：1等，从而使得无定形态锂硅合金颗粒112主要起到嵌脱锂离子的作用，无定形态锂硅合金层12对内核11起到保护和固定作用，并且有利于锂离子传输效果的提高。
在本申请实施方式中，负极材料10的粒径为20nm-20μm。进一步的，负极材料10的粒径为100nm-19μm。更进一步的，负极材料10的粒径为0.5μm-18μm、1μm-17μm、2μm-16μm、3μm-15μm、5μm-13μm或7μm-12μm等。具体的，负极材料10的粒径可以为但不限于50nm、1.5μm、2.8μm、4.5μm、8μm、10μm、12.5μm、14μm、16μm或18μm等。
在本申请实施方式中，负极材料10在室温下的离子电导率在10 -7S·cm -1以上，室温为15℃-30℃。
在本申请实施方式中，负极材料10在室温下的电子电导率在10 -2S·cm -1以上，室温为15℃-30℃。
请参阅图2，为本申请一实施方式提供的制备负极材料的方法流程示意图，包括：
S101：将无定形态Li xSi颗粒分散在玻璃态固体电解质中，得到内核，其中，0＜x≤4.4。
S102：将内核用无定形态Li ySi包覆，得到负极材料，其中，0＜y≤4.4。
在本申请中，可以直接提供非晶态的原料进行混合，也可以通过球磨的方式得到非晶态的原料。在本申请一实施方式中，将无定形态Li xSi颗粒分散在玻璃态固体电解质中包括：将无定形态Li xSi颗粒与玻璃态固体电解质混合均匀即可。在本申请另一实施方式中，将无定形态Li xSi颗粒分散在玻璃态固体电解质中包括：将Li xSi颗粒与固体电解质混合，经球磨混合后，得到无定形态Li xSi颗粒以及玻璃态固体电解质，且无定形态Li xSi颗粒分散在玻璃态固体电解质中。进一步的，球磨混合的转速为150rpm-350rpm，处理时间为1h-5h。更进一步的，球磨混合的转速为200rpm-300rpm，处理时间为2h-4h。通过长时间的高转速球磨可以得到非晶态的原料，并且玻璃态固体电解质之间、以及玻璃态固体电解质和无定 形态Li xSi之间接触性能佳，有利于降低阻抗，提高离子电导率。在本申请又一实施方式中，将无定形态Li xSi颗粒分散在玻璃态固体电解质还进行热处理。通过热处理改善无定形态Li xSi颗粒与玻璃态固体电解质的界面相容性，进一步提升接触性能。在一实施例中，热处理包括以超过10℃/min的速率升温至250℃-400℃，保温10min-60min。具体的，可以为但不限于以超过10℃/min的速率升温至300℃，保温30min。
在本申请实施方式中，将内核11用无定形态Li ySi包覆包括：将Li ySi进行球磨，得到无定形态Li ySi，然后将内核11和无定形态Li ySi混合球磨后，无定形态Li ySi包覆内核11。在本申请一实施例中，球磨的方式可以是湿法球磨或干法球磨。具体的，湿法球磨中溶剂可以包括但不限于甲苯、二甲苯、苯甲醚、庚烷、癸烷、乙酸乙酯、丙酸乙酯、丁酸丁酯、N-甲基吡咯烷酮和丙酮等中的至少一种。在本申请另一实施方式中，球磨的转速为50rpm-250rpm，时间为5min-30min。进一步的，球磨的转速为150rpm-250rpm，时间为20min-30min。
在本申请实施方式中，负极材料10的制备在保护性气体下进行。具体的，保护性气体包括氮气、氦气、氢气等中的至少一种。
本申请的制备方法制备得到的负极材料10的相关参数及作用如上，此处不再赘述。
本申请提供的制备负极材料10的方法可以制备得到上述接触性好、在脱/嵌锂的过程中体积膨胀效应小、循环稳定性好以及电化学性能优异的负极材料，并且工艺简单，易于操作，适用于工业化生产，有利于负极材料的应用。
请参阅图3，为本申请一实施方式提供的全固态锂电池的结构示意图，全固态锂电池包括正极200、负极100以及位于正极200和负极100之间的固态电解质层300，负极100包括上述任一实施方式中的负极材料10。
在本申请实施方式中，负极100包括负极集流体102，以及设置在负极集流体102上的负极材料层101，负极材料层101包括负极材料10。具体的，负极材料层101的厚度可以为但不限于5μm-50μm。
在本申请实施方式中，负极材料层101不含导电剂。这样负极材料层101就可包括含量较多、具有电化学活性的负极材料10，进而使负极100的容量较大、全固态锂电池的能量密度较高。
在本申请实施方式中，负极材料层101还包括粘结剂中的至少一种。其中，粘结剂有助于使负极材料层101牢固固定在负极集流体102上，并使负极材料层101具有一定弹性。在本申请一实施例中，粘结剂可以包括但不限于聚噻吩、聚吡咯、聚四氟乙烯、聚偏氟乙烯、聚乙烯、聚丙烯、聚苯乙烯、聚丙烯酰胺、乙烯-丙烯-二烯共聚树脂、苯乙烯丁二烯橡胶、聚丁二烯、氟橡胶、聚乙烯吡咯烷酮、聚酯树脂、丙烯酸树脂、酚醛树脂、环氧树脂、 聚乙烯醇、羧丙基纤维素、乙基纤维素、聚氧化乙烯、羧甲基纤维素钠和丁苯橡胶中的至少一种。在本申请另一实施例中，粘结剂在负极材料层101中的质量百分含量为0.5％-5％。具体的，粘结剂在负极材料层101中的质量百分含量可以为但不限于1％-5％、1.5％-4.5％、2％-4％或2.5％-3.8％等。
在本申请实施方式中，正极200可以包括正极集流体202和设置在正极集流体202上的正极材料层201。其中，正极材料层201可以包括正极活性材料、导电剂、正极用固态电解质材料、正极用粘结剂。
在本申请实施方式中，正极活性材料包括氧化物型、硫化物型、聚阴离子型以及上述各材料的复合物中的一种或多种。在本申请一实施例中，氧化物型正极活性材料可以包括但不限于TiO 2、Cr 3O 8、V 2O 5、MnO 2、NiO、WO 3、LiMn 2O 4、Li 2CuO 2、LiCo mNi 1-mO 2(0≤m≤1)、LiCo aNi 1-a-bAl bO 2(0≤a≤1，0≤b≤1)、LiFe cMn dG eO 4(G选自Al、Mg、Ga、Cr、Co、Ni、Cu、Zn和Mo中的至少一种，0≤c≤1，0≤d≤1，0≤e≤1，c+d+e＝1)、Li 1+fL 1－g－hH gR hO 2(L、H和R分别独立选自Li、Co、Mn、Ni、Fe、Al、Mg、Ga、Ti、Cr、Cu、Zn、Mo、F、I、S和B中的至少一种，且L、H和R互为不同元素，且-0.1≤f≤0.2，0≤g≤1，0≤h≤1，0≤g+h≤1)等中的至少一种。具体的，氧化物型正极活性材料可以包括但不限于LiCoO 2、LiNiO 2、LiMn 2O 4中的一种或多种。在本申请另一实施例中，硫化物型正极活性材料可以包括但不限于TiS 2、V 2S 3、FeS、FeS 2、WS 2、LiJS i(J选自Ti、Fe、Ni、Cu和Mo中的至少一种，1≤i≤2.5)等中的至少一种。在本申请又一实施例中，聚阴离子型正极活性材料可以包括但不限于LiFePO 4、Li 3V 2(PO 4) 3、Li 3V 3(PO 4) 3和LiVPO 4F中的至少一种。
在本申请实施方式中，正极活性材料的粒径为100nm-500μm。具体的，正极活性材料的粒径可以为但不限于100nm-100μm、100nm-50μm或500nm-50μm等。
在本申请实施方式中，正极活性材料的表面还可以带有包覆层，以优化正极材料层201与固态电解质之间的界面，降低界面阻抗，提高循环稳定性。具体的，正极活性材料表面的包覆层可以包括但不限于LiNbO 3、LiTaO 3、Li 3PO 4、Li 4Ti 5O 12等。
在本申请中，对正极材料层201中的正极用粘结剂没有特别限制。例如可以包括但不限于含氟树脂、聚偏二氟乙烯、聚四氟乙烯、聚乙烯醇、聚烯烃、丁苯橡胶等的至少一种。对正极材料层201中的导电剂没有特别限制，采用本领域现有常规材料即可，如导电剂包括但不限于导电炭黑(如乙炔黑、科琴黑)、碳纳米管、碳纤维和石墨中的至少一种。在本申请一实施例中，正极用粘结剂在正极材料层201中的质量百分比含量为0.01％-10％。具体的，正极用粘结剂在正极材料层201中的质量百分比含量可以为但不限于0.015％-8％、0.02％-7％、0.02％-5％或0.05％-4.5％等。在本申请另一实施例中，导电剂在正极材料层201中的质量百分含量为0.1％-20％。具体的，导电剂在正极材料层201中的质量百分含量可以 为但不限于0.5％-18％、1％-15％、1％-10％或3％-8.5％等。
在本申请实施方式中，上述负极集流体102、正极集流体202独立地选自金属箔材或合金箔材。其中，金属箔材包括但不限于铜、钛、铝、铂、铱、钌、镍、钨、钽、金或银箔材，合金箔材包括但不限于不锈钢、或含铜、钛、铝、铂、铱、钌、镍、钨、钽、金和银中至少一种元素的合金。例如，负极集流体102可以具体为铝箔、正极集流体202可以具体为铜箔。本申请中负极集流体102、正极集流体202的厚度及表面粗糙度可以根据实际需求进行调整。
在本申请实施方式中，固态电解质层300可以由含固态电解质材料和溶剂的浆料涂覆、干燥而成，固态电解质层300的成分包括固态电解质材料。在本申请另一实施方式中，固态电解质层300还可以含有粘结剂，其材质可以选自上述正极材料层201中的粘结剂，在此不再赘述。在本申请一实施例中，固态电解质层300可以通过涂覆的方式与负极材料层101结合，进而固态电解质层300再与带正极材料层201的正极200可以通过压制结合。
在本申请实施方式中，正极用固态电解质材料及固态电解质层300中的固态电解质材料独立地选自钠超离子导体(NASICON)固态电解质、石榴石型固态电解质、钙钛矿型固态电解质和硫系固态电解质中的一种或者多种。固态电解质层300的材质与正极用固态电解质材料相同或不同。例如，固态电解质层的成分选择耐还原的固态电解质材料，以保护负极100的负极材料10，进一步提升负极材料10的循环稳定性。进一步地，在制备固态电解质层300和正极材料层201时，所用的固态电解质材料的粒径可以为1nm-5μm。在本申请一实施例中，NASICON型固态电解质可以包括但不限于LiM 2(PO 4) 3及其掺杂物中的一种或多种，其中M为Ti、Zr、Ge、Sn或Pb，掺杂物采用的掺杂元素选自Mg、Ca、Sr、Ba、Sc、Al、Ga、In、Nb、Ta和V中的一种或多种。在本申请另一实施例中，石榴石型固态电解质的化学式为Li 7+p-q-3uAl uLa 3-pX pZr 2-qY qO 12，其中0＜p≤1，0＜q≤1，0＜u≤1，X选自La、Ca、Sr、Ba和K中的至少一种，Y选自Ta、Nb、W和Hf中的至少一种。在本申请另一实施例中，钙钛矿型固态电解质的化学式为A 1 x1B 1 y1TiO 3、A 1 x2B 2 y2Ta 2O 6、A 3 x3B 3 y3Nb 2O 6或A cE dD eTi fO 3，其中，x1+3y1＝2，0＜x1＜2，0＜y1＜2/3；x2+3y2＝2，0＜x2＜2，0＜y2＜2/3；x3+3y3＝2，0＜x3＜2，0＜y3＜2/3；c+2d+5e+4f＝6，c、d、e、f均大于0；A 1、A 2、A 3独立地选自Li和Na中的至少一种，B 1、B 2、B 3独立地选自La、Ce、Pr、Y、Sc、Nd、Sm、Eu和Gd中的至少一种，E选自Sr、Ca、Ba、Ir和Pt中的至少一种，D选自Nb和Ta中的至少一种。在本申请另一实施例中，硫系固态电解质包括但不限于结晶态的Li rQ sP t1S z、玻璃态Li 2S-P 2S 5和玻璃陶瓷态Li 2S-P 2S 5及其掺杂物中的一种或多种，其中，结晶态的Li rQ sP t1S z中，Q选自Si、Ge和Sn中的一种或多种，r+4s+5t1＝2z，0≤s≤1.5。玻璃态Li 2S-P 2S 5包括Li 2S与P 2S 5组成的不同产物，例如包括Li 7P 3S 11或70Li 2S-30P 2S 5等。
在本申请实施方式中，还提供了制备全固态锂电池的方法，包括：
S201：制备负极100：负极材料10与第一溶剂混合得到负极混合浆料；负极混合浆料涂布在负极集流体102上，经干燥、压制处理后，得到负极100。
S202：制备固态电解质层300：在保护气体存在下，固态电解质材料和第二溶剂混合均匀，得到固态电解质混合浆料，固态电解质混合浆料连续涂布在负极上，干燥后，在负极100上形成固态电解质层300。
S203：制备正极200：将正极活性材料、正极用固态电解质、导电剂、正极用粘结剂和第三溶剂混合均匀，得到正极混合浆料；正极混合浆料涂布在正极集流体202上，干燥、压片处理后，得到正极200。
S204：在保护气体存在下，将带有固态电解质层300的负极100与制得的正极200对齐，贴合极耳，经热压处理、真空密封和等静压压制处理后，得到全固态锂电池。
在本申请实施方式中，第一溶剂、第二溶剂和第三溶剂独立地选自水、乙醇、甲苯、二甲苯、苯甲醚、乙腈、庚烷、癸烷、乙酸乙酯、丙酸乙酯、丁酸丁酯、N-甲基吡咯烷酮、丙酮等中的至少一种。各溶剂的用量一般可以为在配置对应混合浆料中干物料质量的50wt％-400wt％。
在本申请实施方式中，压片可以在但不限于0-5MPa进行辊压处理。
在本申请实施方式中，热压处理的温度可以为但不限于100℃左右，热压处理时间可以为但不限于0.5h-3h；等静压压制的压强可以为但不限于100MPa以上，例如压强为100MPa-300MPa；等静压压制处理的时间可以为但不限于3min-10min。
本申请提供的全固态锂电池，由于包含了上述负极材料10，全固态锂电池的电池容量高、循环性能好，有利于其应用。
下面分多个实施例对本申请实施例进行进一步的说明。
实施例1
一种制备全固态锂电池的方法，包括以下步骤：
(1)负极片的制作
在氩气气氛下，31g的Li 2S、60g的P 2S 5、7g的SiS 2、2g的P 2O 5、1000g的Li 2.3Si共同放置在球磨罐中，加入适量的ZrO 2研磨珠，以200rpm的转速高能球磨2h后转移至电热炉中(保护气氛下)，以不低于10℃/min的升温速度升温至300℃，保持30min，得到内核，内核包括Li 2S、P 2S 5、SiS 2和P 2O 5形成的玻璃态固体电解质，以及分散在其中的无定形态Li 2.3Si颗粒。
将1000g的Li 1.71Si置于球磨罐中，加入适量的ZrO 2研磨珠，以250rpm的转速高能球磨0.5h，得到无定形态的Li 1.71Si合金；将1000g内核、50g无定形态的Li 1.71Si合金以及1000g 甲苯溶剂共同置于球磨罐中，加入适量的ZrO 2研磨珠，以50rpm的速度进行球磨30min，得到负极材料，负极材料为无定形态的Li 1.71Si合金层包覆内核。经过聚焦离子束切割(FIB)颗粒样品并使用扫描电镜(SEM)观察，发现无定形态Li 2.3Si颗粒平均粒径约为50nm，无定形态Li 1.71Si合金层平均厚度约为250nm，负极颗粒整体平均粒径约为1μm。
将1000g负极材料、30g粘结剂SBR橡胶、1500mL甲苯溶液共同放置入分散机中，分散时间30min，形成稳定均一的负极浆料。将负极浆料均匀地间歇涂布在铜箔(宽度160mm，厚度16μm)上，然后373K烘干，经过辊压机压片后得到负极。
(2)固态电解质层的制作
在氩气气氛下，将600g的70Li 2S·30P 2S 5玻璃态固态电解质材料置入含30g丁二烯橡胶粘结剂的1200g的甲苯溶液中，加热搅拌至得到稳定、均一的浆料；将该浆料连续涂布在步骤(1)得到负极上，然后在373K烘干，在负极上形成厚度为50μm的固态电解质层。
(3)正极的制作
将1000g LiCoO 2、51mL乙醇铌、12g乙醇锂、1000mL去离子水和1000mL乙醇进行充分混合，在持续的搅拌下，滴加氨水调节pH至10，将溶液蒸干，将所得粉末在400℃条件下加热8h，得到表面包覆有LiNbO 3的LiCoO 2正极活性材料。
取上述1000g经LiNbO 3包覆的LiCoO 2正极活性材料、150g的Li 10GeP 2S 12固态电解质材料、30g粘结剂丁二烯橡胶、20g乙炔黑、20g碳纤维加入到1500g的甲苯溶剂中，然后在真空搅拌机中搅拌，形成稳定均一的正极混合浆料；将该正极混合浆料均匀地间歇涂布在铝箔(宽度160mm，厚度16μm)上，然后在393K下烘干，经过辊压机压片后，在铝箔上形成厚度为100μm的正极材料层，得到正极。
(4)全固态锂电池的制作
在保护气氛下，将上述正极与带有固态电解质层的负极对齐放置在压片机中，贴合极耳，在100℃下热压1h，使用铝塑膜抽真空密封后，最后在等静压机中于200MPa下压制300s，得到全固态锂电池。
实施例2
一种制备全固态锂电池的方法，其与实施例1大致相同，不同之处在于Li 2.3Si变为Li 4.4Si，Li 1.71Si变为Li 3.75Si，LiNbO 3包覆的LiCoO 2正极活性材料变为TiS 2。经过聚焦离子束切割(FIB)颗粒样品并使用扫描电镜(SEM)观察，发现无定形态Li 4.4Si颗粒平均粒径约为75nm，无定形态Li 3.75Si合金层平均厚度约为350nm，负极颗粒整体平均粒径约为1.3μm。
实施例3
一种制备全固态锂电池的方法，其与实施例1大致相同，不同之处在于采用12.4g的Li 2S、24g的P 2S 5、2.8g的SiS 2、0.8g的P 2O 5、1000g的Li 2.3Si共同放置在球磨罐中，加入 适量的ZrO 2研磨珠，以150rpm的转速高能球磨0.3h后转移至电热炉中(保护气氛下)，以不低于10℃/min的升温速度升温至300℃，保持30min，得到内核，其余步骤不变。经过聚焦离子束切割(FIB)颗粒样品并使用扫描电镜(SEM)观察，发现无定形态Li 2.3Si颗粒平均粒径约为1.2μm，无定形态Li 1.71Si合金层平均厚度约为5μm，负极颗粒整体平均粒径约为30μm。
为突出本申请实施例的有益效果，特提供以下对比例：
对比例1
一种制备全固态锂电池的方法，其与实施例1的不同之处在于使用碳包覆的硅负极材料替换负极材料，其中碳包覆的硅负极材料制备方法包括：将1000g的Si和240g的蔗糖共同置于1000mL去离子水中搅拌均匀，然后在搅拌的过程中加热至100℃，待水分蒸发后取出固形物，在惰性气氛下加热至300℃，得到碳包覆的硅负极材料，碳包覆的硅负极材料直接作为负极，其余步骤不变。
对比例2
一种制备全固态锂电池的方法，其与实施例1的不同之处在于步骤(1)的具体操作如下：将1000g的Si和240g的蔗糖共同置于1000mL去离子水中搅拌均匀，然后在搅拌的过程中加热至100℃，待水分蒸发后取出固形物，在惰性气氛下加热至300℃，得到碳包覆的硅负极材料；将1000g碳包覆的硅负极材料与150g的70Li 2S·30P 2S 5玻璃态电解质材料以及100g乙炔黑、1500mL的甲苯配制成混合浆料，涂覆到铜箔上，经干燥、压片，制得负极，其余步骤不变。
对比例3
一种制备全固态锂电池的方法，其与实施例1的不同之处在于将步骤(1)中的1000g的内核以及50g的无定形态Li 1.71Si直接与30g粘结剂SBR橡胶、1500mL甲苯溶液混合作为负极浆料，950g的内核与50g的无定形态Li 1.71Si之间不进行包覆，其余步骤不变。
对比例4
一种制备全固态锂电池的方法，其与实施例1的不同之处在于步骤(1)中将310g的Li 2S、600g的P 2S 5、70g的SiS 2、20g的P 2O 5共同放置在球磨罐中，加入适量的ZrO 2研磨珠，以200rpm的转速高能球磨2h后转移至电热炉中，以不低于10℃/min的升温速度升温至300℃，保持30min，得到玻璃态固体电解质；取90g玻璃态固体电解质、910g的Li 2.3Si以及50g的Li 1.71Si直接与30g粘结剂SBR橡胶、1500mL甲苯溶液混合作为负极浆料，其余步骤不变。
对比例5
一种制备全固态锂电池的方法，其与实施例1的不同之处在于步骤(1)中得到内核后 就直接用以涂覆负极片，不进行外壳无定形态Li 1.71Si的包覆，其余步骤不变。
性能测试
对上述实施例1-3和对比例1-5中得到的全固态锂电池进行电池循环寿命的测试，测试方法如下：将各实施例和对比例制得的全固态锂电池样品各取20支，在LAND CT 2001C二次电池性能检测装置上，于298±1K条件下，将各电池以0.1C的倍率进行充放电循环测试。
测试步骤如下：搁置10min；恒压充电至4.25V/0.05C截止；搁置10min；恒流放电至3V，即为1次循环，记录下首圈放电容量(使用TiS 2作为正极的，电压上下限分别为3V/0.05C和1V，其余条件相同)。重复上述循环步骤，当循环过程中电池容量低于首次放电容量的80％时，循环终止，循环终止时的循环次数即为电池的循环寿命，每组取平均值，得到的结果如表1所示。
表1各组样品的循环寿命测试数据表
Figure PCTCN2022080644-appb-000001
从表1可以获知，对比例1的放电容量和循环寿命均很差，对比例2-4的放电容量和循环寿命明显低于实施例1-3；采用电解液的锂电池中常用的碳包覆的硅负极材料的对比例1，其电池性能极差，说明该负极材料不太适合于全固态锂电池；但将该碳包覆的硅负极材料与固态电解质混合(对比例2)，所制得的电池性能相较于对比例1有所提升，但仍远远比不上由本申请实施例1-3的负极材料制成的全固态锂电池；不制备内核且不进行包覆，直接进行混合形成的负极材料制得的电池(对比例4)虽然放电容量有所提高，但循环性能仍然不佳；直接采用内核形成的负极材料制得的电池(对比例5)的循环性能较对比例4稍有提高，但放电容量却稍有降低；直接采用内核且不进行包覆形成的负极材料制得的电池(对比例3)的放电容量和循环性能较对比例4稍有提高，但提升幅度不大，远远比不上由本申请实施例1-3的负极材料制成的全固态锂电池的性能。由此表明，采用本申请的负极材料制得的全固态锂电池，其负极放电比容量较高，电池的循环寿命较好，有利于其广泛使用。
上面结合附图对本申请的实施例进行了描述，但是本申请并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本申请的启示下，在不脱离本申请宗旨和权利要求所保护的范围情况下，还可做出很多形式，均属于本申请的保护之内。

Claims (10)

  1. 一种负极材料，其中，所述负极材料包括内核以及包覆所述内核的无定形态锂硅合金层，所述内核包括玻璃态固体电解质以及分散在所述玻璃态固体电解质中的无定形态锂硅合金颗粒，所述无定形态锂硅合金颗粒的材质为Li xSi，0＜x≤4.4，所述无定形态锂硅合金层的材质为Li ySi，0＜y≤4.4。
  2. 如权利要求1所述的负极材料，其中，所述无定形态锂硅合金颗粒与所述无定形态锂硅合金层的质量比为(1-100)：1。
  3. 如权利要求1或2所述的负极材料，其中，所述内核中，所述无定形态锂硅合金颗粒的质量分数为50％-95％。
  4. 如权利要求1-3中任一项所述的负极材料，其中，所述无定形态锂硅合金颗粒的粒径为10nm-1μm；所述无定形态锂硅合金层的厚度为5nm-1μm；所述负极材料的粒径为20nm-20μm。
  5. 如权利要求1-4中任一项所述的负极材料，其中，所述玻璃态固体电解质包括玻璃态氧化物固体电解质和玻璃态硫化物固体电解质中的至少一种。
  6. 如权利要求1-5中任一项所述的负极材料，其中，按摩尔百分比计，所述玻璃态固体电解质包括：
    30mol％-80mol％的Li 2S、10mol％-50mol％的P 2S 5、0mol％-30mol％的SiS 2和0mol％-30mol％的LiA；或
    30mol％-80mol％的Li 2O、10mol％-50mol％的P 2O 5、0mol％-30mol％的SiS 2和0mol％-30mol％的LiA；或
    30mol％-80mol％的Li 2O、20mol％-60mol％的B 2O 3和0mol％-30mol％的LiA；或
    30mol％-80mol％的Li 2S、20mol％-60mol％的SiS 2和0mol％-30mol％的LiA；或
    30mol％-85mol％的Li 2O和15mol％-70mol％的LiA；其中，A为Cl、Br和I中的至少一种。
  7. 一种制备负极材料的方法，其中，包括：
    将无定形态Li xSi颗粒分散在玻璃态固体电解质中，得到内核，其中，0＜x≤4.4；
    将所述内核用无定形态Li ySi包覆，得到负极材料，其中，0＜y≤4.4。
  8. 如权利要求7所述的方法，其中，将所述内核用无定形态Li ySi包覆包括：
    将Li ySi进行球磨，得到所述无定形态Li ySi；
    将所述内核和所述无定形态Li ySi混合球磨后，所述无定形态Li ySi包覆所述内核。
  9. 一种全固态锂电池，其中，包括正极、负极以及位于所述正极和所述负极之间的固 态电解质层，所述负极包括如权利要求1-6中任一项所述的负极材料或采用如权利要求7-8任一项所述的方法制得的负极材料。
  10. 如权利要求9所述的全固态锂电池，其中，所述负极包括负极集流体以及设置在所述负极集流体上的负极材料层，所述负极材料层包括所述负极材料，且所述负极材料层不含导电剂。
PCT/CN2022/080644 2021-03-19 2022-03-14 负极材料及其制备方法和全固态锂电池 WO2022194089A1 (zh)

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