WO2023216940A1 - 一种掺杂氧硅材料及其制备方法和应用 - Google Patents

一种掺杂氧硅材料及其制备方法和应用 Download PDF

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WO2023216940A1
WO2023216940A1 PCT/CN2023/091757 CN2023091757W WO2023216940A1 WO 2023216940 A1 WO2023216940 A1 WO 2023216940A1 CN 2023091757 W CN2023091757 W CN 2023091757W WO 2023216940 A1 WO2023216940 A1 WO 2023216940A1
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oxygen
group
elements
silicon material
doped
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PCT/CN2023/091757
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English (en)
French (fr)
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黄杰
刘冬冬
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四川物科金硅新材料科技有限责任公司
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Priority claimed from CN202210490311.5A external-priority patent/CN117059788A/zh
Priority claimed from CN202210490624.0A external-priority patent/CN117059756A/zh
Priority claimed from CN202210490342.0A external-priority patent/CN115719799A/zh
Application filed by 四川物科金硅新材料科技有限责任公司 filed Critical 四川物科金硅新材料科技有限责任公司
Publication of WO2023216940A1 publication Critical patent/WO2023216940A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/00—Electrodes
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides

Definitions

  • the present application relates to the field of battery technology, specifically to an oxygen-doped silicon material and its preparation method and application.
  • silicon-containing negative electrode materials In the field of batteries, there are many negative electrode materials.
  • silicon-containing negative electrode materials have entered the researchers' field of vision; among them, silicon dioxide and silicon oxide materials prepared from silicon have relatively high It has high theoretical specific capacity, low lithium storage reaction voltage platform, lower volume expansion than pure silicon and low preparation cost, so it has become a type of negative electrode material with great potential to replace graphite.
  • the conductivity of silicon oxide is poor. Although it can be basically solved by carbon coating, silicon oxide will consume more lithium during the cycle to form irreversible phases such as Li 2 O, Li 4 SiO 4 , Li 2 SiO 5 , etc. , resulting in lower initial efficacy.
  • the oxygen in the silicon oxide is combined with the metal in advance, and pre-lithium or other metals are pretreated.
  • lithium due to the high activity of lithium and potassium, lithium can be pre-lithiumized at room temperature or lower temperature, allowing lithium or potassium to be embedded in silicon oxide and combined with oxygen in advance to avoid the combination of lithium and oxygen during the battery charging process to produce irreversible lithium.
  • Oxygen compounds or lithium silicate The advantage of this method is that the temperature of lithium or potassium embedded in silicon oxide is low. It can keep the silicon particle size of the silicon phase produced after pre-lithium being less than 1nm. After optimizing the parameters, it can even be more Small; the shortcomings are also obvious. There is lithium silicate in the particles after pre-lithium.
  • the produced Li 4 SiO 4 and Li 2 SiO 3 have poor water resistance and are alkaline when dissolved in water.
  • the above materials are used in the preparation process of negative electrode slurry. If the stability of the slurry is insufficient, gas may be generated or the silicon oxide particles and binder components may agglomerate and settle.
  • divalent or trivalent metal elements are directly combined with oxygen in silicon oxide to form divalent or trivalent silicates that are insoluble in water, it will effectively avoid dissolution in water during the preparation process of battery slurry and cause residual alkali.
  • the reaction activity between metals or oxides of divalent or trivalent elements and silicon oxide is low (first, the metal bond or the bond between metal and oxygen needs to be broken and reorganized, which requires high energy and high temperature), resulting in its The reaction temperature with silicon oxide is high (generally greater than 900°C).
  • the silicon produced will also migrate and agglomerate, causing the particles to grow.
  • this application provides an oxygen-doped silicon material and its preparation method and application to improve the cycle performance of the battery.
  • the specific technical solutions are as follows:
  • an oxygen-doped silicon material is provided.
  • amorphous in this application is: if a material containing a certain substance does not have a characteristic peak corresponding to the substance in the X-ray diffraction pattern, then the substance is said to be amorphous in the material.
  • the doped oxygen silicon material includes an oxygen silicon material and a metal element doped in the oxygen silicon material; the metal element exists in the oxygen silicon material in the form of a metal amorphous compound; the metal Elements include non-group IA elements or a mixture of non-group IA elements and group IA elements in the IUPAC (Periodic Table of Elements).
  • the doping amount of the metal element is ⁇ , and the range of ⁇ is: 0 ⁇ 1; the doping amount of the non-group IA element is ⁇ , 0 ⁇ ; the group IA element The doping amount is ( ⁇ - ⁇ ).
  • the group IA elements are located in the center area of the doped oxygen silicon material, and the non-group IA elements are located in the center area of the doped oxygen silicon material.
  • External area covers the central area; the external area is the intermediate area from the central area to the surface.
  • the metal amorphous compound includes oxides and/or silicates of metal elements.
  • the non-Group IA elements include at least one of Group IIA elements, Group IIB elements, Group VIIB elements, and Group VIII B elements.
  • the Group IA elements include alkali metals, preferably K and/or Li; the Group IIA elements include Mg and/or Ca; the Group IIB elements include Zn; the Group VIIB elements include Mn; The Group VIII B elements include Fe; preferably, the non-Group IA elements include divalent metals and/or trivalent metals; preferably, the metal elements include K, Li, Mg, Ca, Mn, Fe and Zn of at least one.
  • the oxygen-doped silicon material also contains crystalline silicon; the X-ray diffraction pattern of the oxygen-doped silicon material includes diffraction angles 26° ⁇ 2 ⁇ 30°, 46° ⁇ 2 ⁇ 49°, 54° ⁇ Characteristic peaks at 2 ⁇ 57°; preferably, the characteristic peaks belong to crystalline silicon.
  • the composition of the oxygen-doped silicon material is An-2y ⁇ My ⁇ SiO z ;
  • the main structure of the oxygen-doped silicon material is an amorphous structure of SiO z ; where, 0.7 ⁇ z ⁇ 1.2 , 0 ⁇ n-2y ⁇ z, 0 ⁇ n ⁇ z, 0 ⁇ y ⁇ 0.5z;
  • A is an alkali metal
  • M is a divalent metal; and the metal reducing property of the alkali metal A is greater than the metal reducing property of the divalent metal M ;
  • the content of divalent metal M decreases from the surface to the interior of the composite material
  • the content of alkali metal A decreases from the interior to the surface of the composite material
  • the alkali metal A includes lithium and/or potassium; the metal M includes at least one of magnesium, calcium, manganese, zinc, and iron.
  • the alkali metal A exists in the composite material as an amorphous compound of A; and the metal M exists in the composite material as an amorphous compound of M.
  • silicon is present in the composite material in an amorphous state.
  • the amorphous compound of A includes silicate and/or oxide of A.
  • the amorphous compound of M includes silicates and/or oxides of M.
  • the doped oxygen silicon material further includes a carbon coating layer; the carbon coating layer covers the oxygen silicon material and the metal element.
  • the carbon coating layer covers the entire oxygen-silicon material and metal elements, which not only protects the internal materials, but also increases the conductivity of the oxygen-doped silicon material, achieving double protection of the oxygen-doped silicon material.
  • the mass of the carbon coating layer is 0.1% to 10% of the mass of the oxygen-doped silicon material.
  • a method of preparing the oxygen-doped silicon material as described in any one of the above is provided.
  • the preparation method includes: (1) mixing an oxygen silicon material with a source of Group IA elements to embed alkali metal elements to obtain an oxygen silicon material containing Group IA elements; (2) mixing the oxygen silicon material containing Group IA elements.
  • the oxygen silicon material is mixed with a non-group IA element source, and ion exchange is performed to obtain the doped oxygen silicon material.
  • the silicon-based material includes silicon dioxide and/or silicon oxide; the Group IA elements include alkali metals; and the Group IA element sources include elements, hydrides, borohydrides, and amino groups of Group IA elements.
  • the mass ratio of the oxygen silicon material to the source of group IA elements is 1: (0.001 to 0.9); the mass ratio of the source of non-group IA elements to the source of silicon-based materials containing group IA elements and the source of non-group IA elements is The total mass content is 0.01% to 99%, preferably 5% to 67%.
  • the embedding includes chemical embedding and/or high-temperature sintering embedding.
  • the chemical embedding includes: (1-1) dissolving the source of Group IA elements in an ether solution containing biphenyl and its derivatives to obtain a solution containing Group IA elements; (1-2) dissolving oxygen
  • the silicon material is immersed in a solution containing group IA elements and chemically intercalated to obtain the oxygen silicon material containing group IA elements; preferably, after step (1-2), heat treatment is also included; the heat treatment is to treat the oxygen silicon material containing group IA elements.
  • the oxygen silicon material of group elements is heated; preferably, the heating temperature is 300 to 750°C, and the heating time is 0.5 to 20 hours.
  • the chemical embedding conditions are: temperature is 5-40°C, and time is 1-120 hours.
  • the high-temperature sintering embedding includes: mixing an oxygen-silicon material with a group IA element source and sintering it at a high temperature to obtain the oxygen-silicon material containing group IA elements; preferably, the temperature of the high-temperature sintering is 200 to 800 °C, heating time is 1 ⁇ 20h.
  • the ion exchange refers to embedding non-group IA elements in the oxygen silicon material instead of all or part of the group IA elements to obtain the doped oxygen silicon material; preferably, the conditions for the ion exchange are: temperature The temperature is 150 ⁇ 650°C and the time is 1 ⁇ 48h.
  • the preparation method further includes carbon coating; the carbon coating can be performed before step (1), after step (2), or between step (1) and step (2).
  • the carbon coating conditions are: temperature 600-1000°C, time 0.5h-10h.
  • a negative electrode material including the oxygen-doped silicon material as described in any one of the above.
  • the mass proportion of the oxygen-doped silicon material in the negative electrode material is ⁇ 2%.
  • the negative electrode material further includes a carbon-based material; the carbon-based material is at least one of artificial graphite, natural graphite, soft carbon, hard carbon, and mesocarbon microspheres (MCMB); preferably, the The carbon-based material is artificial graphite and/or natural graphite.
  • the carbon-based material is at least one of artificial graphite, natural graphite, soft carbon, hard carbon, and mesocarbon microspheres (MCMB); preferably, the The carbon-based material is artificial graphite and/or natural graphite.
  • a negative electrode sheet which includes the negative electrode material as described in any one of the above.
  • the negative electrode sheet further includes a binder and a conductive agent.
  • the binder includes at least one of styrene-butadiene rubber (SBR) emulsion, polyvinylidene fluoride, sodium carboxymethylcellulose, lithium carboxymethylcellulose, polyacrylic acid, lithium polyacrylate, and sodium polyacrylate. kind.
  • SBR styrene-butadiene rubber
  • the conductive agent includes at least one of carbon black, conductive graphite, carbon fiber, carbon nanotubes, and graphene.
  • a nonaqueous electrolyte secondary battery including a positive electrode sheet, an electrolyte solution, a separator, and any of the above negative electrode sheets.
  • This application improves the first-efficiency problem of oxygen-silicon material (silicon oxide) through the doping of metal elements, that is, through the doping of metal elements, the metal elements and the oxygen in the silicon oxide material are combined in advance to form Stabilizing compounds, in subsequent battery cycles, make the combination of lithium and oxygen less or no residual combination, ultimately reducing or eliminating the oxygen element in silicon oxide, resulting in a reduction in the efficiency of the battery in the first cycle; after exchanging the non-IA group through the exchange reaction
  • the exchange and substitution of elements with group IA elements greatly reduces the adverse effects of compounds produced only by doping group IA elements, such as alkalinity and instability, and greatly improves the electrical properties of oxygen-silicon materials.
  • the doped non-group IA element compound is located in the outer area of the doped oxygen silicon material, which is not only the surface coating of the particles, but can also be maintained even if the surface is abraded during subsequent battery preparation processes.
  • the stability of the material Secondly, the processing temperature of the non-group IA element compounds doped with IA group elements and the exchange reaction doped is low.
  • the group IA elements and non-group IA element compounds are both in an amorphous state. The existence of surface effects in the amorphous state will There are more lithium ion channels in the material. Since lithium ions are transported quickly in the doped silicon oxide of the present invention, the rate capability of the material can be improved. Therefore, under the same current density, the material capacity is higher.
  • the main structure of the oxygen-doped silicon material is the amorphous structure of SiO z , then the structures of various substances are amorphous, that is, A compounds, M compounds, and silicon are all amorphous.
  • the charge and discharge of the material Lithium ion channels will be formed during the process. Due to its amorphous state, the transmission speed of lithium ions is increased, which can improve the rate capability of the material; and the amorphous silicon particles are small and have good conductivity; furthermore, the amorphous material of this application A and M in battery materials occupy some of the vacancies and sites that combine with oxygen, which can avoid subsequent use in batteries and reduce the loss of battery cathode materials. That is, there is less chance of recombination with oxygen, thus improving the corresponding cycle efficiency. .
  • This application solves the problem of low first efficiency of oxygen-silicon materials by pre-embedding IA group elements, avoids the loss of group IA elements during the cycle, and accordingly improves its first-cycle efficiency, and does not require direct removal.
  • Activity silicates formed by Group IA elements, but through ion exchange, replace Group IA elements, reduce the amount of Group IA element silicates in oxygen silicon materials, and silicic acid formed by non-Group IA elements after ion exchange Salt compounds are more stable than group IA element silicates, thereby enhancing the water resistance of oxygen silicon materials.
  • ion exchange some metals that are less active than group IA elements can be used to replace group IA elements, overcoming the doping of elements that cannot be achieved through redox methods in current technology; in addition, the exchange of non-group IA elements Afterwards, corresponding compounds can be generated with components such as silicon and oxygen to form a coating structure for the partially exchanged Group IA elements.
  • This structure can further promote the stability of the negative active material of the present application, that is, not only reducing the amount of unstable substances , it also coats unstable substances to achieve double protection and greatly improves its water resistance; furthermore, the ion exchange in this application is not only a replacement of the surface, but also a replacement of the IA group elements doped in the entire oxygen silicon material. Replacement is a physical exchange.
  • a doped oxygen silicon material containing crystalline silicon can be generated without changing the state of silicon in the oxygen silicon material, that is, the particle size does not grow, which can improve the cycle performance of the material; at the same time
  • the compound formed after doping group IA elements is in an amorphous state; then non-group IA elements are substituted for all or part of the group IA elements through ion exchange.
  • the transition from the particle surface to the interior can be realized Complete replacement, and the temperature of this ion exchange is low, and it does not change the state of silicon in the oxygen-silicon material; because the compound formed after doping with group IA elements is in an amorphous state, non-group IA elements can replace group IA to the greatest extent element, thereby minimizing the lithium content in the oxygen-doped silicon material, thereby reducing costs.
  • an amorphous structure in which the main structure of the oxygen-doped silicon material is SiO z can be generated, which avoids the transformation of amorphous silicon to crystalline silicon at high temperatures and improves the cycle stability of the material.
  • the compounds of A are also amorphous, so that during subsequent ion exchange, M can replace the A element to the greatest extent until it is completely replaced, greatly reducing the substances unstable to water in the composite material, and
  • the generated M compound has high stability to water and greatly reduces the amount of residual alkali, thus improving the stability of the overall material; in addition, due to the poor reducibility of M relative to A, it is difficult to The M element that enters SiO z can be easily entered through ion exchange, avoiding high energy-consuming methods such as high temperature and high pressure.
  • Figure 1 is a schematic diagram (a) and a partial enlarged diagram (b) of the content distribution of group IA elements and non-group IA elements in the oxygen-doped silicon material provided by this application;
  • Figure 2 is an SEM picture of the oxygen-doped silicon material provided in Example 5 of the present application.
  • Figure 3 is an elemental energy spectrum of the oxygen-doped silicon material provided in Embodiment 5 of the present application.
  • Figure 4 is an XRD pattern of the oxygen-doped silicon material provided in Embodiment 5 of the present application; the abscissa is 2 ⁇ , and the unit is degrees; the ordinate is intensity, and there is no unit;
  • Figure 5 is the first charge and discharge curve of the oxygen-doped silicon material provided in Embodiment 5 of the present application; the abscissa is the specific capacity, in mAh/g; the ordinate is the voltage, in V;
  • Figure 6 is a 40-cycle capacity retention diagram of the oxygen-doped silicon material provided in Embodiment 5 of the present application; the abscissa is the number of cycles, without units; the ordinate is the capacity retention rate, in %.
  • Figure 7 is a schematic diagram of the content and position of alkali metal A and divalent metal M in the oxygen-doped silicon material provided by this application;
  • Figure 8 is an SEM picture of the oxygen-doped silicon material provided in Example 6 of the present application.
  • Figure 9 is an elemental energy spectrum of the oxygen-doped silicon material provided in Embodiment 6 of the present application.
  • Figure 10 is an XRD pattern of the oxygen-doped silicon material provided in Embodiment 6 of the present application; the abscissa is 2 ⁇ , and the unit is degrees; the ordinate is intensity, and there is no unit;
  • Figure 11 is the first charge and discharge curve of the oxygen-doped silicon material provided in Embodiment 6 of the present application; the abscissa is the specific capacity, in mAh/g; the ordinate is the voltage, in V;
  • Figure 12 is a 50-cycle capacity retention rate diagram of the oxygen-doped silicon material provided in Embodiment 6 of the present application; the abscissa is the cycle number, in times; the ordinate is the capacity retention rate, in %;
  • Figure 13 is an SEM image of the oxygen-doped silicon material provided in Example 7 of the present application.
  • Figure 14 is an ICP (inductively coupled plasma spectrum) diagram of the oxygen-doped silicon material provided in Embodiment 7 of the present application;
  • Figure 15 is an XRD pattern of the oxygen-doped silicon material provided in Embodiment 7 of the present application; the abscissa is 2 ⁇ , and the unit is degrees; the ordinate is intensity, and there is no unit;
  • Figure 16 is a first-cycle charge-discharge curve of the oxygen-doped silicon material provided in Embodiment 7 of the present application; the abscissa is the specific capacity, in mAh/g; the ordinate is the voltage, in V;
  • Figure 17 is a 50-cycle capacity retention rate diagram of the oxygen-doped silicon material provided in Embodiment 7 of the present invention.
  • the abscissa is the number of cycles, without units; the ordinate is the capacity retention rate, in %.
  • the oxygen-doped silicon material includes an oxygen silicon material and a metal element doped in the oxygen silicon material; the metal element exists in the oxygen silicon material in the form of a metal amorphous compound.
  • the metal elements include non-group IA elements or a mixture of non-group IA elements and group IA elements in IUPAC (Periodic Table of Elements).
  • amorphous in this application is: if a material containing a certain substance does not have a characteristic peak corresponding to the substance in the X-ray diffraction pattern, then the substance is said to be amorphous in the material.
  • the doping amount of metal elements is ⁇ , and the range of ⁇ is: 0 ⁇ 1.
  • the doping amount refers to the molar ratio of the doping element to the silicon element in the oxygen silicon material.
  • the value of the doping amount ⁇ of the metal element can be 0.001, 0.002, 0.005, 0.009, 0.01, 0.05, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 or any two values any value in between.
  • the doping amount ⁇ of the metal element ranges from 0 ⁇ 0.5.
  • the value of the doping amount ⁇ of the metal element can be 0.001, 0.002, 0.005, 0.009, 0.01, 0.05, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5 or any value between any two values numerical value.
  • the doping amount of non-group IA elements is ⁇ , 0 ⁇ ; the doping amount of the group IA elements is ( ⁇ - ⁇ ).
  • the value range of ⁇ can be less than or equal to 0.2; when ⁇ takes a value of 0.7, the value range of ⁇ can be less than or equal to 0.7; the doping amounts of group IA elements are both ⁇ and The difference of ⁇ , the difference can be zero or a value greater than zero, but it cannot exceed ⁇ .
  • ⁇ can be 0.001, 0.002, 0.005, 0.009, 0.01, 0.05, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 or any value between any two values. But it must be less than or equal to ⁇ .
  • Figure 1(a) is only a schematic diagram, in which the doped oxygen silicon material is shown as a circle.
  • the shape of the oxygen silicon material of the present application is not subject to this limitation and can be elliptical, rectangular, square, regular or irregular. Polygons etc.
  • the oxygen-doped silicon material is divided into a central area and an outer area.
  • the central area contains more group IA elements, and the content gradually decreases along the direction of line a; the outer area contains non-group IA elements.
  • the content is relatively high, and along the direction of line b, the content gradually decreases, and finally borders the central area; at the boundary between the central area and the outer area, non-group IA elements and group IA elements can be contained at the same time, but the non-group IA elements
  • the position is further outward relative to the position of the IA group elements, that is, the non-IA group elements are closer to the edge of the composite material than the surrounding IA group elements, as shown in c and d in Figure 1(b) , where c is a particle of a group IA element, d is a particle of a non-group IA element, and c is always located inside the encircling circle formed by d.
  • c and d are only to show the positions of non-group IA elements and group IA elements, and are not intended to limit non-group IA elements and group IA elements.
  • the oxygen silicon material includes silicon oxide, wherein the silicon oxide is SiO x , where 0.7 ⁇ x ⁇ 1.2; for example, x can be 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79 , 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1.00, 1.01, 1.02, 1.03, 1.04 ,
  • the oxygen-silicon material only contains two elements, oxygen and silicon
  • the compounds that can be formed are at least one of a compound formed with oxygen and a compound formed with silicon and oxygen.
  • the metal amorphous compound includes oxides and/or silicates of metal elements.
  • the metal elements include at least one of Group IA elements, Group IIA elements, Group IIB elements, Group VIIB elements, and Group VIII B elements.
  • the IA group elements include alkali metals, preferably K and/or Li; the IIA group elements include Mg and/or Ca; the IIB group elements include Zn; the VIIB group elements include Mn; the VIII B group
  • the element includes Fe; preferably, the metal element includes at least one of K, Li, Mg, Ca, Mn, Fe and Zn.
  • Compounds of Group IA elements and non-Group IA elements include oxides, silicates, etc. of Group IA elements and non-Group IA elements.
  • the compounds doped with Group IA elements and non-Group IA elements include but are not limited to the above structures.
  • the oxygen-doped silicon material in this application includes two situations, one is entirely amorphous material, the other contains crystalline silicon, and the other parts are amorphous.
  • Oxygen-doped silicon materials contain crystalline silicon and the rest is amorphous.
  • the particle size of crystalline silicon is 0.1 ⁇ 8nm, which can be 0.1nm, 0.2nm, 0.3nm, 0.4nm, 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm , 7nm, 8nm or any value between any two values.
  • the size of the crystalline silicon in this application should not be too large. Excessive size will seriously affect the capacity of the material in this application (the conductivity of the material becomes worse) and the cycleability becomes worse.
  • the X-ray diffraction pattern of the oxygen-doped silicon material includes characteristic peaks at diffraction angles of 26° ⁇ 2 ⁇ 30°, 46° ⁇ 2 ⁇ 49°, and 54° ⁇ 2 ⁇ 57°.
  • This characteristic peak is attributed to crystalline silicon. Since the silicon oxide material has a high temperature during the initial carbon coating process, the silicon agglomeration in the oxygen silicon material crystallizes. In the doped oxygen silicon material of the present application, only the crystal structure of crystalline silicon exists. They are all amorphous structures; therefore, the characteristic peaks appearing in this oxygen-doped silicon material must only be attributed to crystalline silicon.
  • oxygen-doped silicon material is an amorphous material, that is, all parts are amorphous.
  • composition is An -2y ⁇ My ⁇ SiOz ;
  • the main structure of the oxygen-doped silicon material is the amorphous structure of SiOz ; where, 0.7 ⁇ z ⁇ 1.2, 0 ⁇ n-2y ⁇ z, 0 ⁇ n ⁇ z,0 ⁇ y ⁇ 0.5z;
  • A is an alkali metal, M is a divalent metal; and the metal reducing property of the alkali metal A is greater than the metal reducing property of the divalent metal M.
  • the content of divalent metal M decreases from the surface to the interior of the composite material, and the content of alkali metal decreases from the interior to the surface of the composite material.
  • z can be 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.8, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92 , 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1, 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.1 7 , 1.18, 1.19 or any value between any two values.
  • n-2y can be any value less than 1.19, for example, it can be 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.8, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94 , or any two Any value between values.
  • the interior of the oxygen-doped silicon material refers to the center of the oxygen-doped silicon material.
  • the center can be the center of gravity, the center, the inner center or the outer center in the conventional sense.
  • the purpose is to indicate the content distribution of alkali metal A and divalent metal M.
  • the alkali metal occupies more of the central area of the doped oxygen silicon material, and forms a decreasing trend outward, as shown by ⁇ in Figure 7;
  • the divalent metal M occupies the doped outside the oxygen-doped silicon material, and forms a decreasing trend toward the inside of the oxygen-doped silicon material, as shown in Figure 1
  • the outer region refers to the other part of the oxygen-doped silicon material excluding the central region, which is closer to the edge than the central region and includes the edge region.
  • the position of the alkali metal A relative to the position of the divalent metal M is always closer to the inside or at most the same level as the divalent metal closest to the inside, and cannot be closer to the edge than the position of the divalent metal M.
  • the oxygen-doped silicon material can be circular, triangular, rectangular, square or other regular or irregular polygonal shapes.
  • the main structure also contains silicon element, which is also amorphous.
  • the oxygen-doped silicon materials in this application are all amorphous, no obvious characteristic peaks appear in the X-ray diffraction pattern analysis; there is an amorphous bulge curve at the diffraction angle 14° ⁇ 2 ⁇ 40° and the bulge curve The area is S1. There is an amorphous bulge curve at the diffraction angle 40° ⁇ 2 ⁇ 60° and the bulge curve area is S2, 0 ⁇ S2/S1 ⁇ 1.
  • the alkali metal A includes lithium and/or potassium; the divalent metal M includes at least one of magnesium, calcium, manganese, zinc, and iron.
  • the alkali metal A exists in the composite material as an amorphous compound of A; the divalent metal M exists in the composite material as an amorphous compound of M.
  • Si exists in the form of at least one of elemental silicon, silicon oxide, silicon oxide, and silicate.
  • Si exists in a form including elemental silicon; the elemental silicon is in an amorphous state; and the elemental silicon is dispersed in the composite material.
  • the silicon element is located in the main structure of the composite material.
  • the amorphous compound of A includes silicate and/or oxide of A.
  • the silicate of A includes A 2 SiO 3 , A 2 Si 2 O 5 or A 4 SiO 4 .
  • the amorphous compound of M includes silicate and/or oxide of M.
  • the silicate of M includes MSiO 3 , MSi 2 O 5 or M 2 SiO 4 .
  • the bulk phase coating of the material is achieved through the ion-exchange composite material, which avoids the problem of the overall coating layer being broken due to particle collision in the subsequent mixing and the impact of slurry mixing on the material during the subsequent preparation of negative electrode sheets.
  • the D50 of the amorphous battery material is 0.1 to 15 ⁇ m, for example, it can be 0.1 ⁇ m, 0.2 ⁇ m, 0.3 ⁇ m, 0.4 ⁇ m, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m, 0.9 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m , 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 14 ⁇ m, 15 ⁇ m or any value between any two values.
  • the particle size of silicon element is not larger than 1nm, for example, it can be 0.1nm, 0.2nm, 0.3nm, 0.4nm, 0.5nm, 0.6nm, 0.7nm, 0.8nm, 0.9nm, 1nm or any two Any value between values.
  • the doped oxygen silicon material further includes a carbon coating layer; the carbon coating layer covers the oxygen silicon material and the metal element.
  • the carbon coating layer covers the entire oxygen-silicon material and metal elements, which not only protects the internal materials, but also increases the conductivity of the oxygen-doped silicon material, achieving double protection of the oxygen-doped silicon material.
  • the mass of the carbon coating layer is 0.1% to 10% of the mass of the oxygen-doped silicon material, for example, it can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9 %, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or any value between any two values.
  • the mass of the carbon coating layer is 2% to 10% of the mass of the amorphous battery material.
  • the mass of the carbon coating layer is 2% to 5% of the mass of the amorphous battery material.
  • the carbon coating layer includes one or more of hard carbon, soft carbon or carbon nanotubes.
  • the carbon coating layer is located on the outermost part of the entire oxygen-doped silicon material, and plays a protective role to protect the internal composite materials from erosion by external electrolytes or water and other substances, thereby improving the stability of the composite materials; at the same time, due to the coating
  • the coating is a carbon coating, which has good electrical conductivity, so it can also improve the ion conductivity and electronic conductivity of the oxygen-doped silicon material.
  • This embodiment provides a method for preparing an oxygen-doped silicon material.
  • the definitions of the oxygen-doped silicon material in this embodiment are completely consistent with the definitions of the oxygen-doped silicon material in Embodiment 1, so the definition will not be repeated.
  • the preparation method includes: (1) mixing the oxygen silicon material with the IA group element source, embedding alkali metal elements, and obtaining the oxygen silicon material containing the IA group element; (2) mixing the oxygen silicon material containing the IA group element with non-IA Group element sources are mixed and ion exchange is performed to obtain the oxygen-doped silicon material.
  • the oxygen silicon material includes silicon dioxide and/or silicon oxide; the chemical formula of silicon oxide is SiO x , where 0.7 ⁇ x ⁇ 1.2, for example, x can be 0.7, 0.8, 0.9, 1.0, 1.1 , 1.2 or any value between any two values.
  • Group IA elements include alkali metals;
  • Group IA element sources include at least one of Group IA element elements, hydrides, borohydrides, amino compounds, and alkyl compounds, because the Group IA element (alkali metal) source is for Doping in silicon-based materials can be done as long as it is a compound or mixture containing Group IA elements (alkali metals). It is preferably a simple substance or hydride of Group IA elements (alkali metals). After doping, no other impurities are introduced, and Has high pre-embedded efficiency.
  • the alkali metal is preferably potassium and/or lithium, that is, the alkali metal source is preferably a potassium source and/or a lithium source, wherein the potassium source is preferably metallic potassium and/or potassium hydride, and the lithium source includes lithium hydride, metallic lithium, and alkyl lithium. , at least one of lithium aluminum hydride, lithium amide, and lithium borohydride.
  • the non-group IA elements include divalent metals and/or trivalent metals; the non-group IA element sources include at least one of oxides, sulfates, and halides of non-group IA elements.
  • the mass ratio of the oxygen silicon material to the IA group element source is 1: (0.001 ⁇ 0.9), for example, it can be 1:0.001, 1:0.002, 1:0.003, 1:0.004, 1:0.005, 1 :0.006, 1:0.007, 1:0.008, 1:0.009, 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09 , 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or any value between any two values.
  • the mass content of the non-group IA element source in the sum of the mass of the silicon-based material containing the group IA element and the non-group IA element source is 0.01% to 99%, preferably 5% to 67%.
  • the embedding includes chemical embedding and/or high-temperature sintering embedding.
  • the chemical embedding includes: (1-1) dissolving the source of Group IA elements in an ether solution containing biphenyl and its derivatives to obtain a solution containing Group IA elements; (1-2) dissolving oxygen The silicon material is immersed in a solution containing group IA elements and chemically intercalated to obtain the oxygen silicon material containing group IA elements.
  • step (1-2) heat treatment is also included; heat treatment is to heat the oxygen silicon material containing group IA elements.
  • the heating temperature is 300 ⁇ 750°C, and the heating time is 0.5 ⁇ 20h.
  • the heating temperature is 300 ⁇ 750°C, the heating time is 0.5 ⁇ 8h; it can be: the heating temperature is 300 ⁇ 500°C, the heating time is 1 ⁇ 6h; it can be: the heating temperature is 300 ⁇ 550°C, the heating time It is 1h ⁇ 20h.
  • the conditions for chemical embedding are: temperature is 5 ⁇ 40°C, time is 1 ⁇ 120h.
  • the time can be 5 ⁇ 120h or 1h ⁇ 120h;
  • the temperature of chemical embedding can be 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C or any two values in between numerical value.
  • the time of chemical embedding can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h, or Any number between any two numbers.
  • Ether solutions containing biphenyl or polybiphenyl include ether solvent A and substance B; the ether solvent A includes tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. At least one of ether and tetraglyme; the substance B includes biphenyl and its derivatives. Preferably, the substance B is 2-methylbiphenyl, 4,4'-dimethyl At least one kind of biphenyl.
  • Group IA elements alkali metals
  • metal silicate amorphous compounds.
  • the generated silicon is also in an amorphous state, so the entire None of the materials produced crystals.
  • Heat treatment is also included after step (1-2). Heat treatment is required to allow lithium ions to fully diffuse into the entire particle to form a group IA element (alkali metal) silicon compound.
  • Heat treatment is to heat oxygen-silicon materials containing group IA elements (alkali metals).
  • the heating temperature is 300 ⁇ 750°C, and the heating time is 0.5 ⁇ 20h.
  • the heating temperature can be 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C °C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C, 700°C,
  • the heat treatment is performed in an inert atmosphere, which includes at least one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere or a xenon atmosphere.
  • the heat treatment temperature is lower than 800°C, consumes relatively little energy, is environmentally friendly and pollution-free, and is suitable for large-scale production.
  • the temperature of the heat treatment the state of each substance in the silicon-based material containing Group IA elements (alkali metals) can be controlled according to the actual situation. For example, at 300 to 550°C, the amorphous state of the original substance will not be changed, which facilitates follow-up.
  • Ion exchange can replace all silicate compounds of Group IA elements (alkali metals); at a higher temperature of 550 to 750°C, various substances in oxygen-silicon materials containing Group IA elements (alkali metals) will be Changes will produce some crystals, silicon crystals and group IA element (alkali metal) silicate crystals, because due to the existence of some group IA element (alkali metal) silicate crystals, and group IA element (alkali metal) silicate crystals The existence of salt crystals is relatively stable, and it is difficult for M to replace the alkali metal in this part. Therefore, M cannot completely replace the alkali metal embedded in step (1).
  • High-temperature sintering embedding includes: mixing an oxygen-silicon material with a source of group IA elements and sintering at a high temperature to obtain the oxygen-silicon material containing group IA elements.
  • the mixing method is one or more of VCH high mixing, three-dimensional mixing or grinding mixing. Since this high-temperature sintering method involves high temperatures, the heat treatment in chemical embedding can be omitted and lithium ions can be directly diffused evenly.
  • the temperature of high-temperature sintering is 200 ⁇ 800°C, and the heating time is 1 ⁇ 20h.
  • the temperature of high-temperature sintering can be 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C , 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510 °C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690
  • Chemical embedding is suitable for Group IA element (alkali metal) sources that are Group IA element (alkali metal) elements, such as potassium metal and lithium metal; high-temperature sintering embedding is suitable for all Group IA element (alkali metal) sources, including elemental substances and hydrides. wait.
  • Ion exchange means that non-group IA elements are embedded in the oxygen silicon material instead of all or part of the group IA elements to obtain the doped oxygen silicon material.
  • the conditions for ion exchange are: temperature is 150 ⁇ 650°C, time is 1 ⁇ 48h.
  • the temperature is 150 ⁇ 550°C, the time is 1h ⁇ 48h; it can be: the temperature is 200 ⁇ 550°C, the time is 4h ⁇ 40h; it can be: the temperature is 200 ⁇ 650°C, the time is 3 ⁇ 48h.
  • the temperature of ion exchange can be 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C , 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460 °C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C
  • Non-group IA element source to perform a low-temperature ion exchange reaction with an oxygen-silicon material containing group IA elements to completely replace or partially replace the group IA element (alkali metal) silicate with poor water resistance in the material to form an amorphous material that is stable to water.
  • group IA element alkali metal
  • ion exchange is not only surface exchange but also bulk phase exchange, which avoids Only the surface coating treatment may cause the problem of surface coating fragmentation caused by particle collision in subsequent mixing, thereby improving the stability of the negative electrode material when preparing negative electrode slurry and the first use of secondary batteries using the negative electrode material.
  • this ion exchange can reduce the amount of group IA elements (alkali metals), especially lithium in group IA elements (alkali metals).
  • the mixed solution after washing can be used to extract lithium from mature salt lakes Technology that recycles lithium can therefore reduce material costs compared to the method of using only lithium to improve the efficiency of oxygen-silicon materials.
  • the preparation method of the negative active material containing doped metal elements is carried out in a non-oxidizing atmosphere.
  • the non-oxidizing atmosphere includes a vacuum environment or an inert atmosphere; the inert atmosphere is at least one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere or a xenon atmosphere.
  • the ion exchange in step (2) can replace the Group IA elements (alkali metals) in the above-mentioned silicate to generate silicate forms of non-Group IA elements. Since Group IA is in an amorphous state The silicate compounds of elements (alkali metals) are relatively easy to replace. Therefore, non-group IA elements will first be replaced around the silicate compounds of group IA elements (alkali metals). When all group IA elements (alkali metals) When the silicate compounds are all amorphous, non-group IA elements can completely replace group IA elements (alkali metals); when the silicate compounds containing group IA elements (alkali metals) are crystalline, non-crystalline elements will appear at the edge of the crystal.
  • Crystalline silicate compounds of Group IA elements (alkali metals) will be replaced by non-Group IA elements to generate silicates of non-Group IA elements, thereby forming a coating structure for the silicate compounds of non-Group IA elements, further reducing contact with the outside world. s contact.
  • the source of metal non-Group IA elements includes at least one of oxides, halides, and sulfates of metal non-Group IA elements, preferably non-Group IA elements.
  • the source is a halide of a metal non-group IA element.
  • the metal M source includes at least one of an oxide, a halide, and a sulfate of metal M.
  • the M source is a halide of metal M.
  • the metal non-group IA elements include divalent metals and/or trivalent metals.
  • the metal M includes divalent metals and/or trivalent metals.
  • the metal non-group IA element is a divalent metal, that is, the non-group IA element source is a non-group IA element -X 2 , X is preferably Cl, Br or I, the non-group IA element is preferably magnesium and/or calcium, non-IA Group element -X 2 is more preferably MgCl 2 .
  • non-group IA elements replace group IA elements to generate silicates of non-group IA elements
  • group IA elements replace non-group IA elements in the source of non-group IA elements.
  • the generated oxides and halides of group IA elements are , acid salts and other substances, the lower the energy and the more stable the structure, the more thorough the ion exchange will be.
  • the more stable forms of the generated oxides, halides, acid salts, etc. of group IA elements are preferred as sources of non-group IA elements. form.
  • the magnesium source is preferably MgCl 2 .
  • the metal M is a divalent metal, that is, the M source is MX 2 , X is preferably Cl, Br or I, M is preferably magnesium and/or calcium, and MX 2 is more preferably MgCl 2 .
  • M replaces the alkali metal to generate M silicate, and the alkali metal replaces M in the M source.
  • the generated alkali metal oxides, halides, acid salts and other substances have lower energy and more stable structure, then The more complete the ion exchange is, the more stable the generated oxide, halide, acid salt, etc. of the alkali metal is preferably used as the M source.
  • the magnesium source is preferably MgCl 2 .
  • the mass content of the non-group IA element source in the sum of the mass of the silicon-based material containing the group IA element and the non-group IA element source is 0.01% to 99%, preferably 5% to 67%.
  • the mass content of the M source in the sum of the mass of the alkali metal-containing silicon-based material and the M source is 0.01% to 99%, preferably 5% to 67%.
  • the doped oxygen silicon material containing doped metal elements After ion exchange, wash, filter and dry to obtain the doped oxygen silicon material containing doped metal elements; preferably, unreacted non-reacted non-group IA element metal salts and generated group IA element salts are removed by washing and filtering, and then After drying, a silicate compound containing group IA elements and non-group IA elements in the particles is obtained, that is, a doped oxygen silicon material containing doped metal elements.
  • the substance used for washing is at least one of water, ethanol, and methanol, preferably water.
  • the solution and solid are separated by centrifugation or pressure filtration.
  • the solid is a doped oxygen silicon material containing lithium and non-group IA elements; further, the lying drying and spray drying methods are used to obtain granular doped materials containing lithium and non-group IA elements. oxygen silicon material.
  • the preparation method also includes particle shaping; particle shaping can be performed after step (1) and/or after step (2); preferably, the particle shaping includes any one or at least two of crushing, ball milling or classification. The combination. Through particle shaping, the size of particles can be controlled to meet production needs.
  • the preparation method also includes carbon coating; the carbon coating can be performed before step (1), after step (2), or between step (1) and step (2).
  • the oxygen-silicon material can be carbon-coated first, then embedded with group IA elements, and finally ion exchanged with a non-group IA element source; or the oxygen-silicon material can be first embedded with group IA elements, then carbon-coated, and finally with Perform ion exchange with a source of non-group IA elements; or first embed group IA elements into the oxygen silicon material, then perform ion exchange with a source of non-group IA elements, and finally perform carbon coating.
  • Carbon coating is to coat one or more layers of carbon material on the surface of the doped oxygen silicon material, which can increase the conductivity of the doped oxygen silicon material. In addition, it can also form a coating on the doped oxygen silicon material to protect the oxygen doped silicon material from Contact with the outside reduces damage to the oxygen silicon material.
  • the conditions for carbon coating are: temperature 600 ⁇ 1000°C, time 0.5h ⁇ 10h.
  • Carbon coating includes gas phase carbon coating and/or solid phase carbon coating.
  • the method of gas phase carbon coating includes: heating oxygen silicon material, doped oxygen silicon material or oxygen silicon material containing group IA elements to 600-1000°C in a protective atmosphere, flowing in organic carbon source gas, and keeping the temperature for 0.5-10 hours.
  • the protective atmosphere includes at least one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere or a xenon atmosphere.
  • the organic carbon source gas includes hydrocarbons; preferably at least one of methane, ethylene, acetylene or benzene.
  • the method of solid phase carbon coating includes: fusing oxygen silicon material, doped oxygen silicon material or oxygen silicon material containing group IA elements with a carbon source for more than 0.5 hours, and then carbonizing the obtained carbon mixture at 600 to 900°C for 2 to 6h.
  • the above-mentioned fusion is carried out in a fusion machine, and the rotation speed of the fusion machine is 500-3000r/min.
  • the carbon source includes at least one of polymers, sugars, organic acids, and asphalt.
  • the thickness of the carbon coating is 5 to 100nm; for example, it can be 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm or any value between any two values.
  • the doped oxygen silicon material of the present application contains crystalline silicon, the other parts are amorphous.
  • the preparation method includes: (1) coating the oxygen silicon material with carbon to obtain the oxygen silicon material containing the carbon layer; (2) mixing the IA group element source and the oxygen silicon material containing the carbon layer to perform the first doping , obtain the first doped oxygen silicon material; (3) heat treat the first doped oxygen silicon material and mix it with a non-group IA element source, and perform the second exchange doping to obtain the doped oxygen Silicon material.
  • the conditions for carbon coating are: temperature 850 ⁇ 1000°C, time 0.5h ⁇ 5h; optionally, in a device containing the oxygen silicon material, a carbon source is introduced and vapor deposited to obtain oxygen silicon containing a carbon layer Material.
  • the temperature of carbon coating can be 600°C, 650°C, 700°C, 750°C, 800°C, 900°C, 910°C, 920°C, 930°C, 940°C, 950°C, 960°C, 970°C, 980°C, 990 °C, 1000°C or any value between any two values.
  • Carbon coating time can be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 6h, 7h, 8h, 9h , 10h or any value between any two values.
  • the conditions for the first doping are: temperature 5 ⁇ 40°C, time 5 ⁇ 120h.
  • the temperature of the first doping can be 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C or any two values. any value between.
  • the first doping time can be 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h , 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h, 48h, 49h, 50h , 51h, 52h, 53h, 54h, 55h, 56h, 57h, 58h, 59h, 60h, 61h, 62h, 63h, 64h, 65h, 66h, 67h, 68h, 69h, 70h, 80h, 90h, 100h, 110h, 120h Or any value between any two values.
  • the source of Group IA elements includes elements of Group IA elements.
  • the molar ratio of the Group IA element source and the oxygen silicon material is 0.01 to 1:1.
  • the molar ratios of group IA element source and oxygen silicon material are 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1: 1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1 or any ratio between any two ratios.
  • the first doping is chemical intercalation.
  • the solution includes solvent A and substance B;
  • the solvent A includes tetrahydrofuran, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
  • the substance B includes biphenyl and its derivatives.
  • the substance B is at least one of 2-methylbiphenyl and 4,4'-dimethylbiphenyl.
  • the heat treatment conditions after the first doping are: temperature 300 ⁇ 550°C, time 1h ⁇ 20h.
  • the temperature can be 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C °C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C or any ratio between any two ratios;
  • the time can be 1h, 2h, 3h , 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h or any value between any two values.
  • the heat treatment conditions after the first doping are: temperature 400 ⁇ 550°C, time 1h ⁇ 10h.
  • the temperature can be 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C °C or any ratio between any two ratios; time can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or any value between any two values.
  • the conditions for the second doping are: the temperature is 200 ⁇ 550°C and the time is 4h ⁇ 40h.
  • the temperature of the second doping can be 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C , 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500 °C, 510°C, 520°C, 530°C, 540°C, 550°C or any ratio between any two ratios; the time can be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23
  • the source of non-Group IA elements includes at least one of oxides, sulfates, and halides of non-Group IA elements, preferably halides of non-Group IA elements. Since halides do not contain oxygen elements, they are attracted to non-Group IA elements. It is weak and easy to dissociate, and the combination of non-group IA elements and silicate groups in A silicate has lower energy, more stability, and lower reaction temperature.
  • the second doping is to replace some or all of the Group IA elements with non-group IA elements through ion exchange.
  • This overcomes the problem in the existing technology that metals with lower reducing properties cannot replace metals with higher reducing properties.
  • the ion exchange method has mild conditions and low temperature, which will not cause the silicon and/or silicate in the material to agglomerate and increase the particle size;
  • this method allows non-Group IA elements to gradually replace Group IA elements from the surface to the interior during the treatment process, forming a coating on the entire particle.
  • the coating layer formed by internal substitution is different from the overall coating and particle surface coating of other patents.
  • the final coating layer is an amorphous compound of metal elements, it has certain ionic and electronic conductivity, and the substitution layer can be very thick; the external coating of other patented particles is different. It has a crystal structure and does not have strong ionic and electronic conductivity, so it cannot If it is too thick, it will affect the electrochemical performance of the material.
  • the internal replacement package of this patent makes the internal particles tightly bonded and coated, and the bonding force is strong. Therefore, even if a certain amount of wear is caused by stirring and other operations, other particles are protected from damage.
  • the molar ratio of the non-group IA element source to the first doped oxygen silicon material is 0.01 to 2:1.
  • the molar ratios of the non-group IA element source and the first doped oxygen silicon material are 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1 , 0.09:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 1:1, 2:1 or any ratio between any two ratios.
  • non-Group IA elements replace all or part of Group IA elements; when non-Group IA elements replace part of Group IA elements, non-Group IA elements are replaced as the reaction proceeds.
  • Compounds of group elements must be gradually substituted from the surface of the particles to the interior of the particles. When non-group IA elements replace all group IA elements, only non-group IA elements remain. Then the doping amount of non-group IA elements is the doping amount of all metal elements. .
  • the preparation method of the oxygen-doped silicon material is carried out in a non-oxidizing atmosphere.
  • the non-oxidizing atmosphere includes a vacuum environment or an inert atmosphere; the inert atmosphere is at least one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere or a xenon atmosphere.
  • This application first dopes IA group elements to combine with the oxygen in the oxygen-silicon material, consuming lithium in advance and reducing the combination of lithium or other elements with oxygen during the first cycle of the subsequent battery, thereby greatly improving the The first effect problem is solved; then, the IA group elements are completely or partially replaced to reduce the doping amount. On the one hand, the amount that can react with water can be reduced; at the same time, since the non-IA group elements have Water has high stability. Substituting IA group elements can maximize its stability with water and maintain the structural stability of the material. Secondly, the coating replaces the coating layer inside the particles, which has high density and strong bonding. Compared with the overall coating, Covering is more practical. Even if the overall structure is damaged by wear and other operations, each Group IA element and its compounds can be protected in a targeted manner.
  • oxygen-doped silicon material is an amorphous material, that is, all parts are amorphous.
  • the preparation method includes: (1) mixing and stirring the A source and SiO z to obtain the precursor A n ⁇ SiO z that is pre-embedded with A; (2) placing the precursor A n ⁇ SiO z that is pre-embedded A in vacuum or inert Heating in gas; (3) Mix the heated A n ⁇ SiO z, the pre-embedded A precursor, with the M source, and sinter in a vacuum or an inert gas atmosphere to obtain the oxygen-doped silicon material.
  • step (3) After sintering in step (3), it also includes washing and filtering, specifically: washing and filtering the mixture containing the amorphous battery material in a solvent to remove by-products.
  • step (1) it also includes: performing vapor phase carbon deposition on the SiO z surface to obtain carbon-coated SiO z .
  • step (1) the temperature for carbon coating on the SiO z surface is 700°C to 800°C, and the time is 0.5 to 10h;
  • the SiO z surface By performing vapor phase carbon deposition on the SiO z surface, the SiO z surface obtains a carbon coating layer, reducing the contact area with the electrolyte and increasing its conductivity.
  • the carbon coating layer covers the entire composite material, which not only protects the composite material, but also increases the conductivity of the composite material.
  • Vapor deposition refers to depositing carbon source gas on the SiO z surface at 700-800°C for 0.5-10 hours. At 700-800°C, the particle size of Si in SiO z will not change significantly, especially the increase in particle size caused by agglomeration; when the Si particle size is larger, it will affect the subsequent material Cycling performance in batteries.
  • the temperature of deposition can be 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C, 800°C or any value between any two values.
  • the deposition time can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5 h, 10h, or any value between any two values.
  • the flow rate of the carbon source gas is 1L/min ⁇ 3L/min, for example, it can be 1L/min, 1.5L/min, 2L/min, 2.5L/min, 3L/min or any value between any two values.
  • the carbon source gas includes at least one of natural gas, methane, acetylene, propane, benzene and toluene.
  • the vapor deposition process also includes a diluting gas; the diluting gas is used to reduce the content of the carbon source gas and to control the deposition of the carbon source gas to be more uniform.
  • the flow rate of the dilution gas is 1L/min-3L/min, for example, it can be 1L/min, 1.5L/min, 2L/min, 2.5L/min, 3L/min or any value between any two values.
  • the diluting gas includes at least one of argon, nitrogen, neon, helium, krypton, and xenon.
  • Step (1) is to mix the A source and SiO z , put it into the solution, stir for 1 to 72 hours, and filter to obtain the precursor A n ⁇ SiO z that is pre-embedded with A.
  • the mass ratio of the A source to SiO z is (0.1 ⁇ 90):100. More preferably, it is (6-90):100.
  • the mass ratio of the A source to SiO z is 0.1:100, 0.2:100, 0.3:100, 0.4:100, 0.5:100, 0.6:100, 0.7:100, 0.8:100, 0.9:100, 1:100 , 10:100, 20:100, 30:100, 40:100, 50:100, 60:100, 70:100, 80:100, 90:100 or any ratio between any two ratios.
  • Source A is a single substance.
  • the solution includes solvent A and substance B; the solvent A includes at least one of tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. ;
  • the substance B includes biphenyl and its derivatives.
  • Solvent A is preferably ethylene glycol dimethyl ether, and substance B is preferably 2-methylbiphenyl or 4,4’-dimethylbiphenyl.
  • This process produces amorphous A compounds during the chemical embedding of metal A, so that in the subsequent ion exchange process, the M element can replace lithium, lithium or potassium to the greatest extent, thus minimizing the negative electrode activity.
  • Lithium/potassium silicate that is unstable to water is included in the material particles to improve the stability of the negative active material particles to water.
  • step (1) the mixing and stirring temperature of source A and SiO z is 5°C to 40°C, and the time is 1h to 120h.
  • the stirring temperature can be 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C or any value between any two values. .
  • the stirring time can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h , 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h, 39h, 40h, 41h, 42h, 43h, 44h, 45h, 46h, 47h, 48h , 49h, 50h, 51h, 52h, 53h, 54h, 55h, 56h, 57h, 58h, 59h, 60h, 61h, 62h, 63h, 64h, 65h, 66h, 67h, 68h, 69h, 70h, 71h, 72h, 80h , 85h, 90h, 95h, 98h, 100h,
  • the alkali metal A is distributed throughout the space of the composite material.
  • step (3) the M element carries out ion exchange with the A element, completely replacing or partially replacing the amorphous A compound in the material.
  • This application uses an innovative ion exchange method to replace metal A with a metal that is currently less reducible, allowing the material to reduce or eliminate the consumption of irreversible metal A that combines with oxygen during the process of pre-embedding A, thus improving the material's performance. First cycle efficiency.
  • the mass ratio of the M source to the carbon-coated SiO z is (0.01 ⁇ 379):100.
  • the mass ratio of the M source to the carbon-coated SiO z is 0.01:100, 0.05:100, 0.5:100, 1:100, 5:100, 10:100, 12:100, 13:100, 14:100 , 15:100, 16:100, 17:100, 18:100, 19:100, 20:100, 30:100, 40:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100, 110:100, 120:100, 130:100, 140:100, 150:100, 160:100, 170: 100, 180:100, 190:100, 200:100, 300:100, 379:100 or any ratio between any two ratios.
  • the M source includes at least one of an oxide, a halide, and a sulfate of M, preferably a halide of M. Since the halide does not contain oxygen, it is weakly attracted to M ions and is easy to dissociate, and the M element and A The silicate radicals in the silicate have lower energy and are more stable after combining, and the reaction temperature is lowered.
  • step (2) the precursor A n ⁇ SiO z pre-embedded with A is heated at a temperature of 300°C to 500°C for 1 to 6 hours.
  • the temperature can be 300°C, 350°C, 400°C, 350°C, 500°C or any value between any two values;
  • the time can be 1h, 2h, 3h, 4h, 5h, 6h or any value between any two values. Any value.
  • step (3) the sintering temperature is 150°C to 550°C, and the sintering time is 1 to 48 hours.
  • the sintering temperature can be 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300 °C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C or any value between any two values; the sintering time can be 1h, 2h, 3h, 4h, 5h , 6h, 7h, 8h, 9h, 10h, 11h, 12
  • metal M replaces metal A
  • the conditions of this ion exchange method are mild to avoid the impact of high temperature on silicon.
  • the aggregation of silicon increases the particle size of silicon or causes the silicon to transform crystalline silicon.
  • the A compound and M compound before and after ion exchange are both amorphous.
  • M replaces part or all of A, allowing the material to reduce or eliminate the consumption of irreversible A that combines with oxygen during the process of pre-embedding A, so the material can be improved.
  • the first cycle cycle efficiency; and ion exchange is not only surface exchange but also bulk phase exchange, which avoids the problem of surface coating fragmentation caused by particle collision in subsequent mixing during surface coating treatment alone, and improves the performance of the slurry. Stability during mixing.
  • this ion exchange also avoids the energy consumption problem of directly combining metal M with SiO z through high temperature and various effects caused by the increase of silicon particles. It avoids the agglomeration of nano-silicon particles and keeps the silicon in an amorphous state.
  • the preparation method of the amorphous battery material is carried out in a non-oxidizing atmosphere.
  • the non-oxidizing atmosphere includes a vacuum environment or an inert atmosphere; the inert atmosphere is at least one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere or a xenon atmosphere.
  • silicon anode materials there are currently some problems in the preparation of silicon anode materials, such as the use of low-temperature pre-lithium oxide silicon dioxide. Although the silicon size in the pre-lithium material is maintained, the size of the silicon particles in the silicon oxide is less than 1nm. After optimizing the parameters, the silicon particles can even be smaller.
  • This embodiment provides a method for preparing amorphous battery materials, which will reconcile the disadvantages of the above two solutions, utilize the high activity of alkali metal and silicon oxide, and adopt a low-temperature pre-embedded solution, thereby ensuring that the silicon after pre-embedded metal Maintain an amorphous state without agglomeration, and the particle size is less than 1nm.
  • the silicon oxide formed after pre-embedded metal and the M source are subjected to an ion exchange reaction under low temperature conditions to partially or completely replace the lithium in the silicate, reducing the Alkali metal silicate, thereby ensuring low residual alkali or neutrality dissolved in water; and M replaces all or part of A, generating M silicate that is more stable to the electrolyte, making the entire amorphous battery material more stable Enhance and reduce the alkalinity in water, improving the service life of subsequent batteries.
  • SiO z is carbon-coated at a lower temperature to maintain the amorphous characteristics of silicon oxide; then alkali metal is embedded into the carbon-coated silicon oxide using room temperature chemical alkali metal embedding method, and the alkali metal is embedded inside the particles.
  • Form amorphous alkali metal silicate compound particles use the poor crystallinity of the alkali metal silicate compound particles inside the particles to have certain lithium ion conduction characteristics and reduce the binding energy of M and O, and convert the halide of the M element into It is mixed and heated for ion exchange, completely replacing or partially replacing the amorphous alkali metal silicate compound in the material, thereby forming a water-stable coating structure and improving the material stability;
  • the chemical formula after the reaction is: A n-2y ⁇ M y ⁇ SiO z ; among them, 0.7 ⁇ z ⁇ 1.2, 0 ⁇ n-2y ⁇ z, 0 ⁇ y ⁇ 0.5 ⁇ z, since M replaces part A, M is a divalent element, so 0 ⁇ y ⁇ of M 0.5 ⁇ z; atoms are reorganized after the reaction.
  • the temperature is not high and the exchanged M compound has an amorphous structure, which does not affect the agglomeration of nano-silica particles and keeps the silicon in an amorphous state. Therefore, it improves the use of compounds containing this
  • the stability of the negative electrode material of the negative electrode active material particles when preparing the negative electrode slurry, and the first-cycle charge-discharge efficiency and cycle performance of the secondary battery using the negative electrode material is not high and the exchanged M compound has an amorphous structure, which does not affect the agglomeration of nano-silica particles and keeps the silicon in an amorphous state. Therefore, it improves the use of compounds containing this.
  • a negative electrode material including the oxygen-doped silicon material as described in any one of the above.
  • the mass proportion of oxygen-doped silicon in the negative electrode material is ⁇ 2%.
  • Oxygen-doped silicon also includes carbon-based materials.
  • the carbon-based material is at least one of artificial graphite, natural graphite, soft carbon, hard carbon, and mesocarbon microspheres (MCMB); preferably, the carbon-based material is artificial graphite and/or natural graphite.
  • MCMB mesocarbon microspheres
  • a negative electrode sheet which includes the negative electrode material as described in any one of the above.
  • the negative electrode sheet also includes a binder and a conductive agent.
  • the binder includes at least one of styrene-butadiene rubber (SBR) emulsion, polyvinylidene fluoride, sodium carboxymethylcellulose, lithium carboxymethylcellulose, polyacrylic acid, lithium polyacrylate, and sodium polyacrylate.
  • SBR styrene-butadiene rubber
  • the conductive agent includes at least one of carbon black, conductive graphite, carbon fiber, carbon nanotubes, and graphene.
  • a battery including a positive electrode sheet, an electrolyte, a separator, and a negative electrode sheet as described above.
  • the oxygen-doped silicon material in this embodiment contains crystalline silicon, and other parts are amorphous.
  • the doping amount is the molar ratio of the doping element to the silicon element in the oxygen-silicon material.
  • the obtained silicate compound doped with Group IA elements is placed in a tube furnace and heated to 500°C with nitrogen gas for 3 hours and then naturally cooled to obtain a silicate compound doped with Group IA elements with uniform element distribution.
  • non-group IA elements (1kg calcium chloride) and mix it evenly with 1kg of silicate compound doped with group IA elements. Place the mixture in a tube furnace, pass nitrogen in, rise to 450°C, sinter for 20 hours, then cool naturally, and then use Wash, filter, remove impurities with deionized water, and dry to obtain an oxygen-doped silicon material; the metal doping amount is 0.26, of which the calcium doping amount is 0.10 and the lithium doping amount is 0.16.
  • Figure 2 is an SEM image of the oxygen-doped silicon material prepared in Test Example 1. It can be seen from the picture that the particle size of the material is about 6um, and the particle size is relatively uniform;
  • Figure 3 shows the oxygen-doped silicon material prepared in Test Example 1 From the energy spectrum, it can be seen that the distribution positions of the doped and exchanged calcium elements are almost the same as those of silicon and oxygen elements, which indicates that the oxygen silicon material is doped with calcium element;
  • Figure 4 shows the doped oxygen silicon prepared in Experimental Example 1 From the XRD pattern of the material, it can be seen that there are only characteristic peaks of crystalline silicon in the material, and no characteristic peaks of other silicates exist. This indicates that the silicates in the material are in an amorphous state and have X-rays.
  • FIG. 1 The diffraction pattern shows that the crystal size of silicon is 4.6nm;
  • Figure 5 is the first-cycle charge-discharge curve of the oxygen-doped silicon material prepared in Test Example 1. It can be seen that the first-cycle charge capacity of the material is 1478mAh/g. The capacity is 1758mAh/g, and the efficiency in the first cycle is 84.07%;
  • Figure 6 is the capacity retention rate diagram of the oxygen-doped silicon material prepared in Test Example 1 after 50 cycles. It can be seen that the capacity retention rate of the material after 50 cycles is 95.4 %.
  • silicate compound doped with Group IA elements is placed in a tube furnace and heated to 510°C with nitrogen gas for 3 hours and then cooled naturally to obtain a silicate compound doped with Group IA elements with uniform element distribution. .
  • silicate compound doped with Group IA elements is placed in a tube furnace and heated to 490°C with nitrogen gas for 3 hours and then naturally cooled to obtain a silicate compound doped with Group IA elements with uniform element distribution. .
  • silicate compound doped with Group IA elements is placed in a tube furnace and heated to 480°C with nitrogen gas for 3 hours and then naturally cooled to obtain a silicate compound doped with Group IA elements with uniform element distribution. .
  • silicate compound doped with Group IA elements is placed in a tube furnace and heated to 520°C with nitrogen gas for 3 hours and then naturally cooled to obtain a silicate compound doped with Group IA elements with uniform element distribution. .
  • silicate compound doped with Group IA elements is placed in a tube furnace and heated to 500°C with nitrogen gas for 3 hours and then naturally cooled to obtain a silicate compound doped with Group IA elements with uniform element distribution. .
  • silicate compound doped with Group IA elements is placed in a tube furnace and heated to 530°C with nitrogen gas for 3 hours and then cooled naturally to obtain a silicate compound doped with Group IA elements with uniform element distribution. .
  • silicate compound doped with Group IA elements is placed in a tube furnace and heated to 510°C with nitrogen gas for 3 hours and then cooled naturally to obtain a silicate compound doped with Group IA elements with uniform element distribution. .
  • silicate compound doped with Group IA elements is placed in a tube furnace and heated to 520°C with nitrogen gas for 3 hours and then naturally cooled to obtain a silicate compound doped with Group IA elements with uniform element distribution. .
  • LiH powder equivalent to 4% by mass of the silicon oxide particles having the carbon layer was mixed with the silicon oxide particles containing the carbon layer in an argon atmosphere, and stirred with a stirrer. Then, by heat-treating the stirred powder at 740°C in an atmosphere-controlled furnace, lithium was inserted into the silicon oxide particles and modified.
  • modified silicon oxide particles put into a mixed solution of ethanol and aluminum dihydrogen phosphate, stir, filter, dry and remove the ethanol.
  • aluminum dihydrogen phosphate adheres to the surface of the silicon oxide particles and the surface of the carbon layer.
  • the modified silicon oxide particles are coated with aluminum dihydrogen phosphate.
  • silicon-based active material particles composed of silicon oxide particles having a carbon layer and a phosphate coating on the surface were produced. Analysis of the X-ray diffraction pattern revealed that the crystal size of silicon in the silicon-based active material particles was 6.63 nm.
  • solution A1 in which lithium flakes and biphenyl, which is a linear polyphenylene compound, are dissolved in tetrahydrofuran (hereinafter also referred to as THF).
  • THF tetrahydrofuran
  • N2 was bubbled into solution A1 (solution A1 was prepared as follows: after dissolving biphenyl in a THF solvent at a concentration of 1 mol/L, 6 was added to the mixture of THF and biphenyl. mass fraction of lithium flakes.
  • the temperature of the solution when immersing the silicon compound particles was 20° C., and the immersion time was set to 10 hours). Then, the silicon compound particles were obtained by filtration.
  • lithium is inserted into the silicon compound particles.
  • the lithium-inserted silicon compound particles were immersed in a solution (solution B) obtained by dissolving naphthalene in THF (solution B was prepared by dissolving naphthalene in a THF solvent at a concentration of 2 mol/L).
  • solution B was prepared by dissolving naphthalene in a THF solvent at a concentration of 2 mol/L.
  • the temperature of the solution when immersing the silicon compound particles was 20° C., and the immersion time was 20 hours.
  • the silicon compound particles were obtained by filtration.
  • Comparative Example 1 uses aluminum dihydrogen phosphate coating to coat the entire particle after lithium embedding, so that the Comparative Example 1 is smaller and less alkaline than Comparative Example 3.
  • Comparing Test Example 1, Comparative Example 1 and Comparative Example 3 it can be seen that the minimum pH value of Test Example 1 is only 7.6, which is not only lower than the 14 of Comparative Example 3, but also It is lower than 12.6 in Comparative Example 1, which shows that the stability of the material of this patent in water is higher than that of the material without treatment after lithium insertion, and also higher than that of the material that coats the entire particle after lithium insertion.
  • Comparing Test Example 1 and Comparative Example 2 it can be found that the pH value of Comparative Example 2 is 13.6, which is much larger than the 7.6 of Test Example 1. This indicates that a coating of Li 2 CO 3 and LiOH is formed on the surface of the lithium-embedded oxygen silicon material. The coating layer will still make the material appear alkaline in water. Although the coating layer will prevent the dissolution of internal lithium silicate, the Li 2 CO 3 and LiOH on the surface of the material will still appear alkaline in water. On the contrary , the material of the present invention not only forms a coating of the particles from the outside to the inside through exchange, but also forms a bulk coating of the lithium silicate inside the particles, thereby ensuring the stability of the material when stirred in water.
  • the more the first lithium insertion amount (the potassium insertion amount can be converted into the lithium insertion amount according to the molar mass), the higher the first effect of the oxygen silicon material will be; in addition, under certain conditions below, the more the first lithium insertion amount, the reversible capacity of the material will be relatively reduced; it should be noted that when the first lithium insertion amount is higher, that is, when it is greater than or equal to 10%, for example, Test Example 4 When it is 10%, the stability of the material will decrease, resulting in a decrease in first effect. This shows that the material of this patent has a relatively large advantage when the first lithium insertion amount is low.
  • Comparative Example 1 When the amount of lithium is low (less than 10%), the more lithium is inserted, the higher the first effect is. For example, comparing Test Example 1 and Comparative Example 1, it can be seen that Comparative Example 1 has less lithium insertion amount for the first time, so the first effect of 80.15% is smaller than that of Test Example 1 of 84.07%, but at the same time it can It can be seen that the reversible capacity of Comparative Example 1 is 1454mAh/g, which is also lower than the reversible capacity of Test Example 1 of 1478mAh/g, which shows that the reversible capacity of Comparative Example 1 is reduced due to coating; in addition, judging from the 50-week capacity retention rate , 91.6% in Comparative Example 1 is also lower than 95.4% in Test Example 1.
  • Comparative Example 1 makes the particle size of the crystalline silicon in Comparative Example 1 larger to 6.63nm, which is larger than 4.8 in Test Example 1. nm, thus making the cycle performance of Comparative Example 1 worse, and because Comparative Example 1 is coated with phosphate outside the lithium-embedded oxygen-silicon material, the coating layer of the oxygen-silicon material of Comparative Example 1 can easily form on the negative electrode. The slurry cracked and fell off during the preparation process, which exposed the lithium silicate in the material and reduced the cycle performance.
  • Comparative Example 1 Comparative Example 1
  • Comparative Example 2 Comparative Example 2 and Test Example 1
  • the additional coating layer reduces the capacity of the material; 2.
  • the coating layer is prone to cracking and falling off during the preparation of the negative electrode slurry, exposing the lithium silicate in the material, which affects the cycle performance of the battery when used in batteries.
  • Comparing Test Example 1 and Comparative Example 2 both of them embedded 6% metallic lithium for the first time. However, due to the change of part of the lithium in Comparative Example 2 to form Li 2 CO 3 and LiOH, the first-cycle efficiency of Comparative Example 2 was reduced. It is 87.63%, which is even lower than the 84.07% of Test Example 1.
  • Comparing Comparative Example 3 and Test Example 9 it can be seen that both are embedded with 3% mass of metallic lithium for the first time, but the first effect of Comparative Example 3 is only 73.35%, which is far inferior to the first effect of Test Example 9 of 80.46%.
  • the 50-week capacity retention rate of Comparative Example 3 was 77.6%, which was also much lower than that of Test Example 9, which was 95.6%.
  • the material of Comparative Example 3 partially agglomerated during the preparation of the negative electrode slurry, indicating that the first embedded Materials that do not undergo ion exchange after lithium are prone to dissolving lithium silicate in water, making the material unstable in water and making its battery performance worse.
  • Comparative Example 3 without ion exchange cannot be used due to the lack of a coating layer. Protect the silicate part of the lithium in the material, causing it to dissolve in water, and may even generate silica during the process. Therefore, after the silicon dioxide of Comparative Example 3 is embedded with lithium, its first effect is not improved and even reduced. reduce.
  • Comparative Examples 1-3 are lower than Test Examples 1-9, and the lowest of Comparative Example 3 is only 93.7%, which shows that the oxygen content after lithium insertion If the silicon material is not coated, the exposed lithium silicate will affect the cycle performance of the material.
  • the retention rate of Comparative Example 1-2 is also lower than that of the test example because the coating layer of Comparative Example 1-2 is a surface coating. The coating is prone to cracking and falling off due to stirring and collision during the preparation of the negative electrode slurry, exposing the lithium silicate salt in the material, thus affecting the cycle performance.
  • oxygen-doped silicon material is an amorphous material, that is, all parts are amorphous.
  • step (3) Use a heating method to heat the lithium-embedded silica in step (2) at 500°C for 3 hours in a vacuum to make the embedded lithium evenly distributed and form a uniform lithium silicate; then take the M source and heat it with 1kg
  • the final lithium-embedded silicon oxide is mixed evenly, and the mixture is placed in a tube furnace and sintered with nitrogen at 280°C for 36 hours. Then it is naturally cooled, washed and filtered with deionized water to remove magnesium chloride and lithium chloride, and dried to obtain a doped oxygen silicon material. .
  • the flow rates of acetylene in step (1) in test examples 1 to 6 are 1.5L/min, 1.5L/min, 2L/min, 2.5L/min, 1.5L/min, and 1.5L/min respectively; carbon coating The temperatures are 800°C, 800°C, 800°C, 800°C, 760°C, and 700°C respectively; the carbon coating times are 4h, 4h, 3.5h, 3h, 4h, and 4h respectively; steps (2) in test examples 1 to 6
  • the times for chemical lithium insertion at room temperature (about 25°C) were 120h, 72h, 120h, 110h, 60h, and 90h respectively.
  • the SEM image, elemental energy spectrum and X-ray diffraction pattern of the oxygen-doped silicon material prepared in Test Example 1 are shown in Figures 8, 9 and 10.
  • Test Example 1 The particle size of the amorphous battery material prepared in 1 is about 5 ⁇ m; from the EDS energy spectrum shown in Figure 9, it can be seen that the amorphous battery material prepared in Test Example 1 is coated with carbon elements on the outside, and the inside of the material contains not only itself In addition to silicon and oxygen, it also contains magnesium, which shows that magnesium has successfully replaced lithium into the material through ion exchange, and magnesium is distributed evenly inside the particles of the material, which shows that amorphous lithium of silicates to maximize ion exchange.
  • Comparative Example 2 As shown in Table 5, through Comparative Example 1, Comparative Example 2 and Comparative Example 3, it can be seen that the pH value of Comparative Example 2 is 13.6, which is much greater than the 7.0 of Comparative Example 1, indicating that the material after lithium embedding of silicon oxide is significantly better in water. Strong alkalinity; the pH values of Comparative Example 3 and Comparative Example 1 are almost neutral, indicating that the embedded magnesium in silica will not affect the pH value of the material in water; through the test examples 1-6 and Comparative Example 2 According to the data, the pH values of Test Examples 1 to 6 are all between 7 and 9, which is much smaller than 13.6 of Comparative Example 2, which shows that the present invention can effectively reduce the alkalinity of lithium-embedded silica in water through ion exchange.
  • Figures 11 and 12 are respectively the first charge-discharge curve and the 50-week capacity retention rate diagram of Test Example 1. It can be seen from Figure 11 that the first charge capacity and first discharge capacity of Test Example 1 are 1475mAh/g and 1728mAh/g; It can be seen from Figure 12 that, except for the first eight cycles, which fluctuate greatly, there is no obvious fluctuation after that, and after 50 cycles, it is in a relatively stable state. It can be seen that the amorphous material prepared in Test Example 1 of the present application has High 50-week capacity retention rate, and the cycle process is in a stable state.
  • Comparative Example 2 It can be seen from Test Example 2 and Comparative Example 2 that the only difference between the preparation of Comparative Example 2 and Test Example 2 is that Comparative Example 2 did not perform ion exchange after inserting lithium. However, the charge and discharge capacity of Comparative Example 2 is much higher. Lower than that of Test Example 2, and the first effect of Comparative Example 2 is only 73.31%, which is also much lower than 81.75% of Test Example 2 (it should be added that Comparative Example 2 had agglomeration during the preparation of the slurry). In addition, Comparative Example 2 The 50-cycle cycle retention rate of Test Example 2 is only 76.6%, which is much lower than that of Test Example 2, which is 96.3%. This shows that Test Example 2 replaces lithium element with magnesium element due to ion exchange. Compared with silicon oxide that does not undergo ion exchange after lithium insertion, material, improving the stability and cycle performance of the material.
  • Comparing Test Example 2 and Comparative Example 3 it can be seen that Comparative Example 3 did not embed lithium but directly embedded magnesium into the silicon-oxygen material at high temperature.
  • the relative atomic mass of the magnesium element is 24, and the relative atomic mass of the lithium element is 7.
  • Comparative Example 3 The 50-cycle cycle retention rate of Comparative Example 3 is only 85%, which is much lower than the 96.3% of Test Example 2. This shows that the particle size of the crystalline silicon in the silicon-oxygen material of Comparative Example 3 becomes larger due to the high-temperature magnesium embedding, which leads to the cycle of the material. Performance deteriorates.
  • Test Example 1 uses low-temperature lithium insertion and ion exchange at lower temperatures to make the silicon in the silicon-oxygen material an amorphous state, with a particle size of less than 1 nm, so Test Example 1 has better cycle performance when applied to negative electrode materials. It was applied to the cycle performance of the anode material in Comparative Example 3.
  • Example 1 According to the content of this application, the preparation method of Example 1 is specifically described, and the specific description is as follows:
  • the obtained carbon-coated lithium-embedded silica was heat-treated at 500°C for 3 hours in an argon atmosphere.
  • Figure 13 is an SEM image of the oxygen-doped silicon material prepared in Test Example 1. It can be seen from the picture that the particle size of the material is about 6um, and the particle size is relatively uniform;
  • Figure 14 shows the first lithium insertion prepared in Test Example 1
  • the ICP diagram of the oxygen-silicon material after the second ion exchange shows that there is no calcium in the silicon-based material after the first lithium insertion (ICP cannot test the lithium content), and the second ion exchange There is calcium element in the final oxygen silicon material, which shows that the oxygen silicon material is indeed doped with calcium element through lithium insertion and then ion exchange;
  • Figure 15 is the XRD pattern of the doped oxygen silicon material prepared in Test Example 1.
  • acetylene as the carbon source at a flow rate of 1.5L/min
  • argon gas as the diluent gas
  • the obtained lithium-embedded silicon oxide was heat treated at 680°C for 3 hours in an argon atmosphere.
  • the obtained lithium-embedded silicon oxide was heat treated at 650°C for 3 hours in an argon atmosphere.
  • the obtained lithium-embedded silicon oxide was heat-treated at 520°C for 3 hours in an argon atmosphere.
  • the obtained lithium-embedded silicon oxide was heat-treated at 520°C for 3 hours in an argon atmosphere. , and then obtain the lithium-doped oxygen silicon material.
  • Mg powder 120g Mg powder, that is, Mg accounts for the mixture The proportion is 12%.
  • After mixing for 30 minutes in a VC mixer put it into a box furnace with 0.1MPa Ar atmosphere and treat it at 1000°C for 12 hours.
  • the doped oxygen silicon materials, SP, CMC and SBR prepared in the test example and comparative example 1 and comparative example 3 were prepared in a mass ratio of 75:15:5:5 and coated on an 8 ⁇ m copper foil. Dry in a blast oven at 60°C for 2 hours, then cut out a number of ⁇ 12mm pole pieces and put them into a vacuum oven at 110°C for 7 hours to dry.
  • the test equipment is used for the charge and discharge test on the LAND battery test system of Wuhan Lanhe Electronics Co., Ltd.
  • the test conditions are: room temperature, discharge according to 0.1C, 0.02C steps in the first three weeks to 5mV, 0.1C constant current charging to 1.5V, 0.1C/0.1C charge and discharge cycle for 40 weeks after the fourth week (the material specific capacity is calculated as: charging capacity/negative active material mass; the battery efficiency in the first week is calculated as: Battery charging specific capacity in the first week/Battery discharge specific capacity in the first week)
  • the first effect of Comparative Example 1 is only 73.35%, which is far lower than the 81.54% of Test Example 6.
  • the 50-week capacity retention rate of Comparative Example 1 is 77.6%, which is also far lower than Test Example 6.
  • Comparative Example 1 showed partial agglomeration during the preparation of negative electrode slurry but did not appear in Test Example 6, which shows that materials that do not perform ion exchange after the first lithium insertion are prone to lithium dissolution in water
  • the silicate makes the material unstable in water, and also makes its battery performance worse. Comparing the performance tests of the two, it can be seen that the material of the present invention performs ion exchange after lithium embedding, which can effectively improve the oxygen-silicon material. efficiency and cycle performance, and the coating formed by ion exchange can improve the stability of the material.
  • the first charge capacity and the first discharge capacity of 1834mAh/g show that the material capacity of this patent, which first embeds lithium and then embeds magnesium through ion exchange, will be much higher than directly doping magnesium; secondly, the 40-week capacity retention rate of Comparative Example 2 The value of 90.1% is lower than that of Test Example 3, which is 97.6%. This indicates that Comparative Example 2 has poor cycle performance due to the larger particle size of the crystalline silicon in its material due to the high temperature treatment at 1000°C.

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Abstract

本申请提供了一种掺杂氧硅材料及其制备方法和应用，掺杂氧硅材料包括氧硅材料和掺杂于氧硅材料内的金属元素；所述金属元素以金属非晶化合物的形式存在于所述氧硅材料中；所述金属元素包括IUPAC(元素周期表)中的非IA族元素或非IA族元素与IA族元素的混合。本申请通过离子交换的方法使得还原性较低的非IA族元素取代了部分或全部IA族元素，提高该掺杂氧硅材料在水中的稳定性，也提高了使用该材料组装的电池的首周充放电效率和循环效率。

Description

一种掺杂氧硅材料及其制备方法和应用 技术领域
本申请涉及电池技术领域，具体涉及一种掺杂氧硅材料及其制备方法和应用。
技术背景
在电池领域，存在较多负极材料，但是随着人们对高能量密度电池的需求日益增加，含硅的负极材料进入研究者的视野；其中，二氧化硅和硅制备的氧化亚硅材料具有较高的理论比容量，较低的储锂反应电压平台，低于纯硅的体积膨胀且制备成本低廉，因此成为替代石墨的极具潜力的一类负极材料。氧化亚硅的导电性较差，虽然可以通过碳包覆基本解决，但氧化亚硅在循环过程中会消耗较多的锂生成Li2O、Li4SiO4、Li2SiO5等不可逆物相，导致其首效较低。
为了提高氧化亚硅首次效率，通过提前让氧化亚硅中的氧和金属结合，预锂或者预其他金属的方法。但是由于锂和钾高活性，在室温或者更低温度，都能预锂，提前让锂或者钾嵌入氧化亚硅中和其中的氧结合，避免电池充电过程中锂和氧的结合生产不可逆的锂氧化合物或者锂的硅酸盐，该方法的优点为锂或者钾嵌入氧化亚硅中的温度低，可以保持预锂后，生产硅相的硅颗粒尺寸小于1nm，优化参数后甚至能做到更小；缺点也比较明显，预锂后颗粒中存在硅酸锂，生产的Li4SiO4和Li2SiO3的耐水性较差，溶于水中显碱性，上述材料在制备过程负极浆料过程中，浆料的稳定性不足，可能会出现有气体产生或者发生硅氧化物的颗粒与粘结剂成分凝集而沉降的现象。
但是如果直接采用二价或者三价金属元素与氧化亚硅中的氧结合，形成不溶于水的二价或者三价硅酸盐，将有效避免电池浆料制备过程中在水中溶解，造成残碱问题，然而二价或者三价元素的金属或者氧化物和氧化亚硅反应的活性低(首先需要将金属键或者金属和氧的键断开和重组，能需能量高，温度高)，造成其和氧化亚硅反应温度高(一般情况大于900℃)，二价或者三价金属元素和氧结合或者形成硅酸盐结合过程中，同时将伴随生产的硅也进行着迁移团聚导致颗粒长大，使得制备出高首周效率的氧化硅中存在结晶的二价或者三价金属元素硅酸盐晶体和硅晶体，较大的硅晶体将影响材料的循环性能。
因此，需要一种能够提高含硅负极材料首效、能够提高含硅负极材料稳定性、且减少硅颗粒长大的一种物质或方法，用于提高电池的循环性能。
发明内容
为了解决上述问题，本申请提供了一种掺杂氧硅材料及其制备方法和应用，用于提高电池的循环性能，具体的技术方案如下：
根据本申请的一方面，提供了一种掺杂氧硅材料。
本申请中非晶的定义为：含有某物质的材料在X射线衍射图中没有该物质相对应的特征峰，则称该物质在该材料中为非晶态。
可选地，所述掺杂氧硅材料包括氧硅材料和掺杂于氧硅材料内的金属元素；所述金属元素以金属非晶化合物的形式存在于所述氧硅材料中；所述金属元素包括IUPAC(元素周期表)中的非IA族元素或非IA族元素与IA族元素的混合。
可选地，所述金属元素的掺杂量为α，α的范围为：0<α≤1；所述非IA族元素的掺杂量为β，0<β≤α；所述IA族元素的掺杂量为(α-β)。
可选地，在所述掺杂氧硅材料中，若同时掺杂IA族元素与非IA族元素，IA族元素位于掺杂氧硅材料中心区域，非IA族元素位于掺杂氧硅材料的外部区域；所述外部区域包覆所述中心区域；所述外部区域为中心区域至表面的中间区域。
可选地，所述金属非晶化合物包括金属元素的氧化物和/或硅酸盐。
可选地，所述非IA族元素包括IIA族元素、IIB族元素、VIIB族元素、VIII B族元素中的至少一种。
可选地，所述IA族元素包括碱金属，优选为K和/或Li；所述IIA族元素包括Mg和/或Ca；所述IIB族元素包括Zn；所述VIIB族元素包括Mn；所述VIII B族元素包括Fe；优选地，所述非IA族元素包括二价金属和/或三价金属；优选地，所述金属元素包括K、Li、Mg、Ca、Mn、Fe和Zn中的至少一种。
可选地，所述掺杂氧硅材料还含有晶体硅；所述掺杂氧硅材料的X射线衍射图谱包括衍射角26°<2θ<30°、46°<2θ<49°、54°<2θ<57°的特征峰；优选地，所述特征峰归属于晶体硅。
可选地，所述掺杂氧硅材料的组成为An-2y·My·SiOz；所述掺杂氧硅材料的主体结构为SiOz的非晶结构；其中，0.7<z<1.2，0≤n-2y<z，0＜n<z，0<y<0.5z；A为碱金属，M为二价金属；且碱金属A的金属还原性大于二价金属M的金属还原性；
可选地，当0<n-2y<z时，二价金属M的含量由复合材料表面至内部递减，碱金属A的含量由复合材料内部至表面递减。
可选地，所述碱金属A包括锂和/或钾；金属M包括镁、钙、锰、锌、铁中的至少一种。
可选地，所述碱金属A以A的非晶化合物存在于所述复合材料中；所述金属M以M的非晶化合物存在于所述复合材料中。
可选地，硅以非晶状态存在于所述复合材料中。
可选地，所述A的非晶化合物包括A的硅酸盐和/或氧化物。
可选地，所述M的非晶化合物包括M的硅酸盐和/或氧化物。
可选地，所述掺杂氧硅材料还包括碳包覆层；所述碳包覆层包覆所述氧硅材料和所述金属元素。
碳包覆层包覆整个氧硅材料和金属元素，不仅可以对其内部材料起保护作用，还可以增加掺杂氧硅材料的导电性，实现对于掺杂氧硅材料的双重保护。
可选地，所述碳包覆层的质量为掺杂氧硅材料质量的0.1％～10％。
根据本申请的另一方面，提供了一种制备如上任一所述的掺杂氧硅材料的方法。
可选地，所述制备方法包括：(1)将氧硅材料与IA族元素源混合，进行碱金属元素的嵌入，得到含有IA族元素的氧硅材料；(2)将含有IA族元素的氧硅材料与非IA族元素源混合，进行离子交换，得到所述掺杂氧硅材料。
可选地，所述硅基材料包括二氧化硅和/或氧化亚硅；所述IA族元素包括碱金属；所述IA族元素源包括IA族元素的单质、氢化物、硼氢化物、氨基化合物、烷基化合物；所述非IA族元素包括二价金属和/或三价金属；所述非IA族元素源包括非IA族元素的氧化物、硫酸盐、卤化物中的至少一种。
可选地，所述氧硅材料与IA族元素源的质量比为1:(0.001～0.9)；所述非IA族元素源在含有IA族元素的硅基材料与非IA族元素源的质量之和的质量含量为0.01％～99％，优选为5％～67％。
可选地，所述嵌入包括化学嵌入和/或高温烧结嵌入。
可选地，所述化学嵌入包括：(1-1)将IA族元素源溶解于含有联苯及其衍生物的醚类溶液中，得到含IA族元素的溶液；(1-2)将氧硅材料浸渍于含IA族元素的溶液中，进行化学嵌入，得到所述含有IA族元素的氧硅材料；优选地，在步骤(1-2)之后还包括热处理；所述热处理是对含有IA族元素的氧硅材料进行加热；优选地，加热温度为300～750℃，加热时间为0.5～20h。
可选地，所述化学嵌入的条件为：温度为5～40℃，时间为1～120h。
可选地，所述高温烧结嵌入包括：将氧硅材料与IA族元素源混合，高温烧结，得到所述含有IA族元素的氧硅材料；优选地，所述高温烧结的温度为200～800℃，加热时间为1～20h。
可选地，所述离子交换是指非IA族元素替代全部或部分IA族元素嵌入所述氧硅材料中，得到所述掺杂氧硅材料；优选地，所述离子交换的条件为：温度为150～650℃，时间为1～48h。
可选地，所述制备方法还包括进行碳包覆；所述碳包覆可在步骤(1)之前、步骤(2)之后或步骤(1)与步骤(2)之间进行。
可选地，所述碳包覆的条件为：温度600～1000℃，时间为0.5h～10h。
根据本申请的又一方面，提供了一种负极材料，包括如上任一所述的掺杂氧硅材料。
可选地，所述掺杂氧硅材料在负极材料中的质量比例为≥2％。
可选地，所述负极材料还包括碳系材料；所述碳系材料为人造石墨、天然石墨、软碳、硬碳、中间相炭微球(MCMB)中的至少一种；优选的，所述碳系材料为人造石墨和/或天然石墨。
根据本申请的再一方面，提供了一种负极片，所述负极片包括如上任一所述的负极材料。
可选地，所述负极片还包括粘结剂、导电剂。
可选地，所述粘结剂包括丁苯橡胶(SBR)乳液、聚偏氟乙烯、羧甲基纤维素钠、羧甲基纤维素锂、聚丙烯酸、聚丙烯酸锂、聚丙烯酸钠的至少一种。
可选地，所述导电剂包括炭黑、导电石墨、碳纤维、碳纳米管、石墨烯中的至少一种。
根据本申请的再一方面，提供了一种非水电解质二次电池，包括正极片、电解液、隔膜和如上任一所述的负极片。
与现有技术相对比，本申请具有以下优点：
(1)本申请通过金属元素的掺杂，提升了氧硅材料(氧化亚硅)的首效问题，即，通过金属元素的掺杂，使得金属元素和氧化亚硅材料中的氧提前结合形成稳定化合物，在后续电池循环中，使得锂和氧的结合较少或根本没有余量结合，最终降低或者消除氧化亚硅中氧元素造成电池的首周效率降低；在通过交换反应将非IA族元素与IA族元素进行交换取代，极大的降低了仅由IA族元素掺杂生成的化合物带来的不利影响，例如碱性、不稳定等问题，极大的提升了氧硅材料的电学性能和使用寿命；另外，由于交换替换造成掺杂的非IA族元素化合物位于掺杂氧硅材料的外部区域，不仅是颗粒表面包覆，即使在后续电池制备过程表面受到磨损等操作中也能保持材料的稳定性，其次，IA族元素掺杂以及交换反应掺杂的非IA族元素化合物处理温度低，IA族元素和非IA族元素化合物均为非晶状态，非晶状态的存在表面效应会使材料中存在较多的锂离子通道，由于锂离子在本发明的掺杂氧化亚硅中传输速度快，从而可以提高材料的倍率性，因此在相同电流密度情况下，材料容量发挥较高。
如果掺杂氧硅材料的主体结构为SiOz的非晶结构，那么各种物质的结构均为非晶态，即A的化合物、M的化合物以及硅均为非晶态，材料的充放电的过程中会形成锂离子通道，由于其非晶状态使得锂离子的传输速度提升，从而可以提高材料的倍率性；并且非晶态的硅颗粒小，导电性好；再者，本申请的非晶电池材料中A和M占据了部分与氧结合的空点和位点，可以避免后续应用在电池时降低对于电池正极材料的损耗，即较少几率可再与氧结合，因此提高相应的循环效率。
(2)本申请通过IA族元素的预嵌，解决氧硅材料了首效低问题，避免了循环过程中对IA族元素的损耗，相应的提高了其首周效率，并且不需要直接脱除活性，IA族元素形成的硅酸盐，而是通过离子交换，替换IA族元素，降低氧硅材料中IA族元素硅酸盐的量，并且离子交换后的非IA族元素形成的硅酸 盐化合物相对于IA族元素硅酸盐更加稳定，从而增强了氧硅材料的耐水性。通过离子交换，可以使得一些相对于IA族元素活性较低的金属，实现对IA族元素的置换，克服了目前技术中通过氧化还原法无法实现的元素的掺杂；另外，非IA族元素交换后，能够通过与硅氧等成分生成相应的化合物，对于部分交换后的IA族元素，形成包覆结构，该结构能够进一步促进本申请负极活性物质的稳定性，即不仅减少不稳定物质的量，还对不稳定物质进行包覆，实现双重保护，大大提高其耐水性；再者，本申请的离子交换不仅仅是表面的替换，而是对于整个氧硅材料中掺杂的IA族元素的替换，即属于体相交换。如果控制低温预嵌IA族元素中的温度，可以生成含有晶体硅的掺杂氧硅材料的，不改变氧硅材料中硅的状态，即粒径不长大，可以提升材料的循环性能；同时使得IA族元素掺杂后形成的化合物处于非晶状态；接着通过离子交换的方式，将非IA族元素替代全部或部分IA族元素，随着时间和温度的提升，可以实现从颗粒表面到内部的完全替代，且该离子交换的温度较低，也不改变氧硅材料中硅的状态；由于IA族元素掺杂后形成的化合物处于非晶状态，非IA族元素能够最大程度的替换IA族元素，从而最大程度的减少掺杂氧硅材料中的锂的含量，从而降低成本。
如果控制低温预嵌碱金属A中的温度，可以生成掺杂氧硅材料的主体结构为SiOz的非晶结构，避免了高温时造成非晶硅向晶体硅的转变，可以提高材料的循环稳定性；同时由于低温使得A的化合物也均为非晶态，从而在后续离子交换时，M能够最大程度的替换A元素，直至全部替换，大大降低该复合材料中对水不稳定的物质，并且生成的M的化合物具有较高的对水的稳定性，且大大减少了残碱的量，因此可以提高整体材料的稳定性；另外，由于M相对于A的还原性较差，使得原本很难进入SiOz中的M元素可以较为方便的通过离子交换进去，避免了高温高压等高耗能的方法。
附图说明
图1为本申请提供的掺杂氧硅材料中IA族元素和非IA族元素的含量分布示意图(a)和局部放大图(b)；
图2为本申请实施例5提供的掺杂氧硅材料的SEM图片；
图3为本申请实施例5提供的掺杂氧硅材料的元素能谱图；
图4为本申请实施例5提供的掺杂氧硅材料的XRD图；横坐标为2θ，单位为度；纵坐标为强度，无单位；
图5为本申请实施例5提供的掺杂氧硅材料的首次充放电曲线图；横坐标为比容量，单位为mAh/g；纵坐标为电压，单位为V；
图6为本申请实施例5提供的掺杂氧硅材料的40周容量保持率图；横坐标为循环周次，无单位；纵坐标为容量保持率，单位为％。
图7为本申请提供的掺杂氧硅材料中碱金属A和二价金属M的含量及位置的示意图；
图8为本申请实施例6提供的掺杂氧硅材料的SEM图片；
图9为本申请实施例6提供的掺杂氧硅材料的元素能谱图；
图10为本申请实施例6提供的掺杂氧硅材料的XRD图；横坐标为2θ，单位为度；纵坐标为强度，无单位；
图11为本申请实施例6提供的掺杂氧硅材料的首次充放电曲线；横坐标为比容量，单位为mAh/g；纵坐标为电压，单位为V；
图12为本申请实施例6提供的掺杂氧硅材料的50周容量保持率图；横坐标为循环周次，单位为次；纵坐标为容量保持率，单位为％；
图13为本申请实施例7提供的掺杂氧硅材料的SEM图；
图14为本申请实施例7提供的掺杂氧硅材料的ICP(电感耦合等离子光谱)图；
图15为本申请实施例7提供的掺杂氧硅材料的XRD图；横坐标为2θ，单位为度；纵坐标为强度，无单位；
图16为本申请实施例7提供的掺杂氧硅材料的首周充放电曲线图；横坐标为比容量，单位为mAh/g；纵坐标为电压，单位为V；
图17为本发明实施例7提供的掺杂氧硅材料的50周容量保持率图；横坐标为循环周次，无单位；纵坐标为容量保持率，单位为％。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚明了，下面对本申请进行进一步详细说明。但是应该理解，此处所描述仅仅用以解释本申请，并不用于限制本申请的范围。
除非另有定义，本文所使用的所有的技术术语和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同，本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在限制本申请。本文中所使用的试剂和仪器均商购可得，所涉及的表征手段均可参阅现有技术中的相关描述，本文中不再赘述。
为了进一步了解本申请，下面结合最佳实施例对本申请作进一步的详细说明。
实施例1
本实施例提供了一种掺杂氧硅材料，掺杂氧硅材料包括氧硅材料和掺杂于氧硅材料内的金属元素；所述金属元素以金属非晶化合物的形式存在于所述氧硅材料中；所述金属元素包括IUPAC(元素周期表)中的非IA族元素或非IA族元素与IA族元素的混合。
本申请中非晶的定义为：含有某物质的材料在X射线衍射图中没有该物质相对应的特征峰，则称该物质在该材料中为非晶态。
金属元素的掺杂量为α，α的范围为：0<α≤1。
其中，掺杂量是指掺杂元素与氧硅材料中的硅元素的摩尔比。
金属元素的掺杂量α的取值可以为0.001、0.002、0.005、0.009、0.01、0.05、0.09、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0或任意两个数值之间的任意数值。
可选地，所述金属元素的掺杂量α的取值范围为0<α≤0.5。
可选地，所述金属元素的掺杂量α的取值可以为0.001、0.002、0.005、0.009、0.01、0.05、0.09、0.1、0.2、0.3、0.4、0.5或任意两个数值之间的任意数值。
非IA族元素的掺杂量为β，0<β≤α；所述IA族元素的掺杂量为(α-β)。
是指，当α取值为0.2时，β的取值范围可以小于等于0.2；当α取值为0.7时，β的取值范围可以小于等于0.7；IA族元素的掺杂量均为α和β的差值，该差值可以为零或大于零的数值，但是也不能超过α。
β的取值范围可以0.001、0.002、0.005、0.009、0.01、0.05、0.09、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0或任意两个数值之间的任意数值。但是要小于或等于α。
图1(a)仅为其中的一个示意图，将掺杂氧硅材料示意为圆形，但是本申请的氧硅材料的形状不受该限制，可为椭圆、长方形、正方形以及规则或不规则的多边形等。如图1所示，将掺杂氧硅材料分为中心区域和外部区域，中心区域中IA族元素的含量较多，且沿着线a的方向，含量逐渐减少；外部区域中非IA族元素的含量较多，沿着线b的方向，含量逐渐减少，最终与中心区域接壤；在中心区域与外部区域的接壤处，可以同时含有非IA族元素与IA族元素，但是非IA族元素的位置相对于IA族元素的位置，更加靠外，即非IA族元素相对于其周围的IA族元素，与复合材料边缘的距离更小，具体如图1(b)中的c和d所示，其中，c为IA族元素的一个粒子，d为非IA族元素的一个粒子，c始终位于d形成的包围圈的里面。c和d仅为展示非IA族元素与IA族元素的位置，不作为对于非IA族元素与IA族元素的限定。
氧硅材料包括有氧化亚硅，其中，所述氧化亚硅为SiOx，其中，0.7<x<1.2；例如，x可以为0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.80、0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.90、0.91、0.92、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1.00、1.01、1.02、1.03、1.04、
1.05、1.06、1.07、1.08、1.09、1.10、1.11、1.12、1.13、1.14、1.15、1.16、1.17、1.18、1.19或任意两个数值之间的任意一个数值。
由于氧硅材料中仅含有氧和硅两种元素，因此，当掺杂金属元素时，可以形成的化合物分别是与氧形成的化合物、与硅和氧形成的化合物中的至少一种。优选地，所述金属非晶化合物包括金属元素的氧化物和/或硅酸盐。
所述金属元素包括IA族元素、IIA族元素、IIB族元素、VIIB族元素、VIII B族元素中的至少一种。
所述IA族元素包括碱金属，优选为K和/或Li；所述IIA族元素包括Mg和/或Ca；所述IIB族元素包括Zn；所述VIIB族元素包括Mn；所述VIII B族元素包括Fe；优选地，所述金属元素包括K、Li、Mg、Ca、Mn、Fe和Zn中的至少一种。
IA族元素、非IA族元素的化合物包括IA族元素、非IA族元素的氧化物、硅酸盐等，该IA族元素、非IA族元素掺杂后的化合物包括但不限于上述结构。
当金属元素中不包括IA族元素时，即仅含有非IA族元素，金属元素的掺杂量等于非IA族元素的掺杂量，即β＝α；当金属元素中包括非IA族元素与IA族元素的混合时，金属元素的掺杂量为非IA族元素的掺杂量与IA族元素的掺杂量之和，即β<α，非IA族元素的掺杂量为β，IA族元素的掺杂量为(α-β)。
本申请的掺杂氧硅材料包括两种情况，一种全是非晶材料，一种含有晶体硅，其他部分为非晶。
掺杂氧硅材料含有晶体硅，其他部分为非晶。
晶体硅的粒径为0.1～8nm，可以为0.1nm、0.2nm、0.3nm、0.4nm、0.5nm、0.6nm、0.7nm、0.8nm、0.9nm、1nm、2nm、3nm、4nm、5nm、6nm、7nm、8nm或任意两个数值之间的任意一个数值。
本申请中晶体硅的尺寸不宜过大，过大会严重影响本申请材料的容量发挥(材料导电性变差)和循环性变差。
所述掺杂氧硅材料的X射线衍射图谱包括衍射角26°＜2θ＜30°、46°＜2θ＜49°、54°＜2θ＜57°的特征峰。
该特征峰归属于晶体硅。由于氧化亚硅材料在最开始的碳包覆的过程中温度较高使得氧硅材料中的硅团聚结晶化，在本申请的掺杂氧硅材料中，仅仅存在晶体硅这一晶体结构，其他均为非晶结构；因此，该掺杂氧硅材料中出现的特征峰必然仅仅归属于晶体硅。
掺杂氧硅材料为非晶材料时，即各个部分均为非晶。
其组成为An-2y·My·SiOz；所述掺杂氧硅材料的主体结构为SiOz的非晶结构；其中，0.7<z<1.2，0≤n-2y<z，0＜n<z，0<y<0.5z；A为碱金属，M为二价金属；且碱金属A的金属还原性大于二价金属M的金属还原性。
当0<n-2y<z时，二价金属M的含量由复合材料表面至内部递减，碱金属的含量由复合材料内部至表面递减。
可选地，z可以为0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.8、0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.9、0.91、0.92、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1、1.01、1.02、1.03、1.04、1.05、1.06、1.07、1.08、1.09、1.10、1.11、1.12、1.13、1.14、1.15、1.16、1.17、1.18、1.19或任意两个数值之间的任意数值。
当z为1.19时，n-2y可以为小于1.19的任意数值，例如可以为0、0.01、0.02、0.03、0.04、0.05、0.06、0.07、0.08、0.09、0.1、0.2、0.3、0.4、0.5、0.6、0.71、0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79、0.8、0.81、0.82、0.83、0.84、0.85、0.86、0.87、0.88、0.89、0.9、0.91、0.92、0.93、0.94、0.95、0.96、0.97、0.98、0.99、1、1.01、1.02、1.03、1.04、1.05、1.06、1.07、1.08、1.09、1.10、1.11、1.12、1.13、1.14、1.15、1.16、1.17、1.18或任意两个数值之间的任意数值。
当0<n-2y<z时，碱金属A和二价金属M均位于所述主体结构中，二价金属M的含量由复合材料表面至内部递减，碱金属的含量由掺杂氧硅材料内部至表面递减；当n-2y＝0时，碱金属A的含量为零，也就是不存在碱金属A，即只有二价金属M位于主体结构中。
掺杂氧硅材料内部是指从掺杂氧硅材料的中心，该中心可以是常规意义上的重心、中心、内心或外心，其目的是要指明碱金属A和二价金属M含量分布的不同，即当0<n-2y<z时，碱金属占据掺杂氧硅材料中心区域较多，且向外形成递减的趋势，如图7中的○所示；二价金属M占据掺杂氧硅材料外部区域，且向掺杂氧硅材料内部方向形成递减的趋势，如图1中的所示；所述外部区域是指掺杂氧硅材料除去中心区域的其他部分，相对于中心区域，更靠近边缘，且包含有边缘区域。但是碱金属A所处的位置相对于二价金属M的位置，始终更加靠近里面或者最多与最靠近里面的二价金属处于同一水平线，不能相对于二价金属M的位置更加靠近边缘。
图7中的和○仅为举例示意，并不代表该物质真实的形态，且图1仅为示意碱金属A和二价金属M的分布情况，对于图1中的形状和大小均不限制本申请的保护范围。掺杂氧硅材料可以圆形、三角形、长方形、正方形或其他规则或不规则的多边形。
所述主体结构中还含有硅单质，硅单质也是非晶态。
由于本申请的掺杂氧硅材料均为非晶态，因此在X射线衍射图分析中，没有出现明显的特征峰；在衍射角14°<2θ<40°存在一个非晶鼓包曲线且鼓包曲线面积为S1，在衍射角40°<2θ<60°存在一个非晶鼓包曲线且鼓包曲线面积为S2，0<S2/S1<1。
所述碱金属A包括锂和/或钾；二价金属M包括镁、钙、锰、锌、铁中的至少一种。
所述碱金属A以A的非晶化合物存在于所述复合材料中；所述二价金属M以M的非晶化合物存在于所述复合材料中。
Si存在的形式包括单质硅、氧化硅、氧化亚硅、硅酸盐中的至少一种。优选地，Si存在的形式包括单质硅；所述单质硅为非晶态；所述单质硅分散于复合材料中。优选地，硅单质位于复合材料的主体结构中。
A的非晶化合物包括A的硅酸盐和/或氧化物，优选地，A的硅酸盐包括A2SiO3、A2Si2O5或A4SiO4。
M的非晶化合物包括M的硅酸盐和/或氧化物，优选地，M的硅酸盐包括MSiO3、MSi2O5或M2SiO4。通过离子交换的复合材料实现材料体相包覆，避免了在后续的混料中可能存在颗粒碰撞导致的整体包覆层破碎的问题以及后续制备负极片时浆料混合对于该材料的影响。
非晶电池材料的D50为0.1～15μm，例如可以为0.1μm、0.2μm、0.3μm、0.4μm、0.5μm、0.6μm、0.7μm、0.8μm、0.9μm、1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm或任意两个数值之间的任意数值。
硅单质由于其非晶结构，其粒径不大于1nm，例如可以为0.1nm、0.2nm、0.3nm、0.4nm、0.5nm、0.6nm、0.7nm、0.8nm、0.9nm、1nm或任意两个数值之间的任意数值。
所述掺杂氧硅材料还包括碳包覆层；所述碳包覆层包覆所述氧硅材料和所述金属元素。
碳包覆层包覆整个氧硅材料和金属元素，不仅可以对其内部材料起保护作用，还可以增加掺杂氧硅材料的导电性，实现对于掺杂氧硅材料的双重保护。
所述碳包覆层的质量为掺杂氧硅材料质量的0.1％～10％，例如可以为0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％、1％、2％、3％、4％、5％、6％、7％、8％、9％、10％或任意两个数值之间的任意数值。
优选地，所述碳包覆层的质量为非晶电池材料质量的2％～10％。
优选地，所述碳包覆层的质量为非晶电池材料质量的2％～5％。
如果包覆的碳层较多，则会影响锂离子的传导速率，并且对电子传导也存在一定的问题，若碳层较少，包覆效果不明显，对于其包覆的氧硅材料的保护力度不行。
所述碳包覆层包括硬碳、软碳或碳纳米管中的一种或多种。
该碳包覆层位于整个掺杂氧硅材料的最外部，承担着保护的作用，使其内部的复合材料免受外部电解质或水等物质的侵蚀，提高复合材料的稳定性；同时由于该包覆层为碳包覆层，具有良好的导电性能，因此也可以提高该掺杂氧硅材料的离子导电性和电子导电性。
实施例2
本实施例提供了一种制备掺杂氧硅材料的方法，本实施例中的掺杂氧硅材料与实施例1中的掺杂氧硅材料限定完全一致，因此不再重复限定。
制备方法包括：(1)将氧硅材料与IA族元素源混合，进行碱金属元素的嵌入，得到含有IA族元素的氧硅材料；(2)将含有IA族元素的氧硅材料与非IA族元素源混合，进行离子交换，得到所述掺杂氧硅材料。
可选地，所述氧硅材料包括二氧化硅和/或氧化亚硅；氧化亚硅的化学式为SiOx，其中，0.7≤x≤1.2，例如x可以为0.7、0.8、0.9、1.0、1.1、1.2或任意两个数值之间的任意一个数值。
IA族元素包括碱金属；IA族元素源包括IA族元素的单质、氢化物、硼氢化物、氨基化合物、烷基化合物中的至少一种，由于该IA族元素(碱金属)源是为了在硅基材料中进行掺杂，只要是含有IA族元素(碱金属)的化合物或混合物均可，优选为IA族元素(碱金属)的单质、氢化物，掺杂后，不引入其他杂质，且具有较高的预嵌的效率。
碱金属优选为钾和/或锂，即碱金属源优选为钾源和/或锂源，其中，钾源优选为金属钾和/或氢化钾，锂源包括氢化锂、金属锂、烷基锂、氢化铝锂、氨基锂、硼氢化锂中的至少一种。
所述非IA族元素包括二价金属和/或三价金属；所述非IA族元素源包括非IA族元素的氧化物、硫酸盐、卤化物中的至少一种。
可选地，所述氧硅材料与IA族元素源的质量比为1:(0.001～0.9)，例如可以为1:0.001、1:0.002、1:0.003、1:0.004、1:0.005、1:0.006、1:0.007、1:0.008、1:0.009、1:0.01、1:0.02、1:0.03、1:0.04、1:0.05、1:0.06、1:0.07、1:0.08、1:0.09、1:0.1、1:0.2、1:0.3、1:0.4、1:0.5、1:0.6、1:0.7、1:0.8、1:0.9或任意两个数值之间的任意数值。
非IA族元素源在含有IA族元素的硅基材料与非IA族元素源的质量之和的质量含量为0.01％～99％，优选为5％～67％。
可选地，所述嵌入包括化学嵌入和/或高温烧结嵌入。
可选地，所述化学嵌入包括：(1-1)将IA族元素源溶解于含有联苯及其衍生物的醚类溶液中，得到含IA族元素的溶液；(1-2)将氧硅材料浸渍于含IA族元素的溶液中，进行化学嵌入，得到所述含有IA族元素的氧硅材料。
在步骤(1-2)之后还包括热处理；热处理是对含有IA族元素的氧硅材料进行加热。
加热温度为300～750℃，加热时间为0.5～20h。
例如可以：加热温度为300～750℃，加热时间为0.5～8h；可以为：加热温度为300℃～500℃，加热时间为1～6h；可以为：加热温度为300～550℃，加热时间为1h～20h。
化学嵌入的条件为：温度为5～40℃，时间为1～120h。
例如可以：时间为5～120h或1h～120h；
化学嵌入的温度可以为5℃、6℃、7℃、8℃、9℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃或任意两个数值之间的任意数值。
化学嵌入的时间可以为1h、2h、3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h、21h、22h、23h、24h、25h、26h、27h、28h、29h、30h、31h、32h、33h、34h、35h、36h、37h、38h、39h、40h、41h、42h、43h、44h、45h、46h、47h、48h、49h、50h、51h、52h、53h、54h、55h、56h、57h、58h、59h、60h、61h、62h、63h、64h、65h、66h、67h、68h、69h、70h、71h、72h或任意两个数值之间的任意数值。
含有联苯或多联苯的醚类溶液包括醚类溶剂A和物质B；所述醚类溶剂A包括四氢呋喃、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚中的至少一种；所述物质B包括联苯及其衍生物，优选的，所述物质B为2-甲基联苯、4,4’-二甲基联苯中的至少一种。
通过化学嵌入的方式，可以使得IA族元素(碱金属)的预嵌在较低温度时发生，可以避免硅基材料中硅团聚长大的问题，并且不需要直接脱除活性IA族元素(碱金属)的硅酸盐。并且化学嵌入，可以使得IA族元素(碱金属)嵌入氧硅材料中，形成IA族元素(碱金属)的硅酸盐化合物为非晶化合物，同时生成的硅也是出于非晶态，从而整个材料均没有晶体的产生。
在步骤(1-2)之后还包括热处理。需要通过热处理让锂离子充分扩散到整个颗粒内部，形成IA族元素(碱金属)硅化合物。
热处理是对含有IA族元素(碱金属)的氧硅材料进行加热。加热温度为300～750℃，加热时间为0.5～20h。加热温度可以为300℃、310℃、320℃、330℃、340℃、350℃、360℃、370℃、380℃、390℃、400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃、610℃、620℃、630℃、640℃、650℃、660℃、670℃、680℃、690℃、700℃、710℃、720℃、730℃、740℃、750℃或任意两个数值之间的任意数值；加热时间可以为0.5h、0.6h、0.7h、0.8h、0.9h、1h、2h、3h、4h、5h、6h、7h 、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h或任意两个数值之间的任意数值。
该热处理在惰性气氛中进行，惰性气氛包括氮气气氛、氦气气氛、氖气气氛、氩气气氛、氪气气氛或氙气气氛中的至少一种。
该热处理温度低于800℃，耗能相对较少，环境友好无污染，适合进行大规模生产。通过控制热处理的温度，可以根据实际情况控制含有IA族元素(碱金属)的硅基材料中各个物质的状态，如在300～550℃时，不会改变原有物质的非晶体状态，便于后续离子交换，可以将IA族元素(碱金属)的硅酸盐化合物进行全部替代；在550～750℃时，处于较高温度，会使得含有IA族元素(碱金属)的氧硅材料中各个物质发生改变，会产生部分晶体，硅晶体和IA族元素(碱金属)硅酸盐晶体，因为由于部分IA族元素(碱金属)硅酸盐晶体的存在，且IA族元素(碱金属)硅酸盐晶体存在较为稳定，M很难将这部分中的碱金属进行替代，因此M不能完全替代步骤(1)中嵌入的碱金属。
高温烧结嵌入包括：将氧硅材料与IA族元素源混合，高温烧结，得到所述含有IA族元素的氧硅材料。混合的方法为VCH高混、三维混料或研磨混料中的一种或多种。由于该高温烧结的方式存在高温，因此可以省略化学嵌入中的热处理，直接将锂离子扩散均匀。
高温烧结的温度为200～800℃，加热时间为1～20h。
高温烧结的温度可以为200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃、290℃、300℃、310℃、320℃、330℃、340℃、350℃、360℃、370℃、380℃、390℃、400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃、610℃、620℃、630℃、640℃、650℃、660℃、670℃、680℃、690℃、700℃、710℃、720℃、730℃、740℃、750℃、760℃、770℃、780℃、790℃、800℃或任意两个数值之间的任意数值；高温烧结的时间可以为1h、2h、3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h或任意两个数值之间的任意数值。
化学嵌入适用于IA族元素(碱金属)源为IA族元素(碱金属)的单质，例如金属钾、金属锂；高温烧结嵌入适用于所有IA族元素(碱金属)源，包括单质、氢化物等。
离子交换是指非IA族元素替代全部或部分IA族元素嵌入所述氧硅材料中，得到所述掺杂氧硅材料。
离子交换的条件为：温度为150～650℃，时间为1～48h。
例如可以为：温度为150～550℃，时间为1h～48h；可以为：温度为200～550℃，时间为4h～40h；可以为：温度为200～650℃，时间为3～48h。
离子交换的温度可以为150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃、290℃、300℃、310℃、320℃、330℃、340℃、350℃、360℃、370℃、380℃、390℃、400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃、610℃、620℃、630℃、640℃、650℃或任意两个数值之间的任意数值；离子交换的时间可以为1h、2h、3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h、21h、22h、23h、24h、25h、26h、27h、28h、29h、30h、31h、32h、33h、34h、35h、36h、37h、38h、39h、40h、41h、42h、43h、44h、45h、46h、47h、48h或任意两个数值之间的任意数值。
用非IA族元素源与含有IA族元素的氧硅材料进行低温离子交换反应，完全替换或者部分替换材料中耐水性差的IA族元素(碱金属)硅酸盐，形成对水稳定的非晶的非IA族元素化合物。该方法简单易于产业化且由于低温不会导致氧硅材料中的硅会变大，从而保证了材料的循环稳定性没有受到影响；此外采用离子交换不仅是表面交换同时存在体相交换，避免了仅仅表面包覆处理在后续的混料中可能存在颗粒碰撞导致的表面包覆破碎的问题，从而提高了将该负极材料制备负极浆料时的稳定性以及使用该负极材料的二次电池的首周充放电效率和循环性能；再者，该离子交换能降低IA族元素(碱金属)用量，尤其是IA族元素(碱金属)中的锂，洗涤后的混合溶液可以采取成熟的盐湖提取锂技术，回收锂，因此和仅采用锂来提升氧硅材料效率的方法来说，可以降低材料成本。
该含有掺杂金属元素的负极活性物质的制备方法在非氧化性气氛下进行。
所述非氧化性气氛包括真空环境或惰性气氛；所述惰性气氛为氮气气氛、氦气气氛、氖气气氛、氩气气氛、氪气气氛或氙气气氛中的至少一种。
目前市面上将硅基材料进行低温预锂，虽然解决了预锂过程中形成硅团聚长大的问题，但带来了产物硅酸锂在水中溶解的问题；而高温预镁虽然解决了硅酸盐溶解问题，但同时带来了预镁过程中硅团聚长大的问题。但是申请在步骤(1)的IA族元素(碱金属)嵌入后，会生成IA族元素(碱金属)的硅酸盐化合物，例如Li4SiO4和Li2SiO3，该硅酸盐化合物耐水性较差，所以步骤(2)的离子交换，可以将上述硅酸盐中的IA族元素(碱金属)进行替代，生成非IA族元素的硅酸盐形式，由于处于非晶状态的IA族元素(碱金属)的硅酸盐化合物比较容易替代，因此，非IA族元素会首先位于IA族元素(碱金属)的硅酸盐化合物周围进行替代，当全部的IA族元素(碱金属)的硅酸盐化合物均为非晶态时，非IA族元素可以将IA族元素(碱金属)完全替代；当存在IA族元素(碱金属)的硅酸盐化合物为晶体时，晶体边缘处得到非晶IA族元素(碱金属)的硅酸盐化合物会被非IA族元素替代生成非IA族元素的硅酸盐，从而对非IA族元素的硅酸盐化合物形成包覆结构，进一步降低与外界的接触。
所述金属非IA族元素源包括金属非IA族元素的氧化物、卤化物、硫酸盐中的至少一种，优选非IA族元 素源为金属非IA族元素的卤化物。所述金属M源包括金属M的氧化物、卤化物、硫酸盐中的至少一种，优选M源为金属M的卤化物。
所述金属非IA族元素包括二价金属和/或三价金属。所述金属M包括二价金属和/或三价金属。
所述金属非IA族元素为二价金属，即非IA族元素源为非IA族元素-X2，X优选为Cl、Br或I，非IA族元素优选为镁和/或钙，非IA族元素-X2更优选为MgCl2。离子交换后，非IA族元素替代IA族元素生成非IA族元素的硅酸盐，IA族元素替代非IA族元素源中的非IA族元素，当生成的IA族元素的氧化物、卤化物、酸盐等物质，能量越低，结构越稳定，则该离子交换进行的越彻底，因此优选生成的IA族元素的氧化物、卤化物、酸盐等较为稳定形式作为非IA族元素源的形式。例如，如果生成的LiCl相较于MgCl2更加稳定，则该离子交换程度会更大，非IA族元素替换Li则越多，那么镁源则优选为MgCl2。所述金属M为二价金属，即M源为MX2，X优选为Cl、Br或I，M优选为镁和/或钙，MX2更优选为MgCl2。离子交换后，M替代碱金属生成M的硅酸盐，碱金属替代M源中的M，当生成的碱金属的氧化物、卤化物、酸盐等物质，能量越低，结构越稳定，则该离子交换进行的越彻底，因此优选生成的碱金属的氧化物、卤化物、酸盐等较为稳定形式作为M源的形式。例如，如果生成的LiCl相较于MgCl2更加稳定，则该离子交换程度会更大，M替换Li则越多，那么镁源则优选为MgCl2。
所述非IA族元素源在含有IA族元素的硅基材料与非IA族元素源的质量之和的质量含量为0.01％～99％，优选为5％～67％。M源在含有碱金属的硅基材料与M源的质量之和的质量含量为0.01％～99％，优选为5％～67％。
离子交换后，进行洗涤过滤干燥，得到所述含有掺杂金属元素的掺杂氧硅材料；优选地，通过洗涤过滤除去未反应的非IA族元素金属盐和生成的IA族元素盐，再进行干燥得到颗粒中含有IA族元素和非IA族元素的硅酸盐化合物，即含有掺杂金属元素的掺杂氧硅材料。
洗涤所用的物质为水、乙醇、甲醇中的至少一种，优选为水。
采用离心或者压滤方式分离溶液和固体，固体为含有锂和非IA族元素的掺杂氧硅材料；进一步采用趴式干燥、喷雾干燥方式得到颗粒状的含有锂和非IA族元素的掺杂氧硅材料。
所述制备方法还包括颗粒整形；可以在步骤(1)之后和/或步骤(2)之后进行颗粒整形；优选地，所述颗粒整形包括破碎、球磨或分级中的任意一种或至少两种的组合。通过颗粒整形可以控制颗粒的尺寸等，满足生产的需求。
制备方法还包括进行碳包覆；所述碳包覆可在步骤(1)之前、步骤(2)之后或步骤(1)与步骤(2)之间进行。
即可以先将氧硅材料进行碳包覆，再进行IA族元素嵌入，最后与非IA族元素源进行离子交换；或者先对氧硅材料进行IA族元素嵌入，然后进行碳包覆，最后与非IA族元素源进行离子交换；或者先对氧硅材料进行IA族元素嵌入，然后与非IA族元素源进行离子交换，最后进行碳包覆。碳包覆是在掺杂氧硅材料表面包覆一层或多层碳材料，可以增加掺杂氧硅材料的导电性，另外也可以对掺杂氧硅材料形成包覆，保护氧硅材料避免与外面的接触，减少对氧硅材料的损伤。
碳包覆的条件为：温度600～1000℃，时间为0.5h～10h。
碳包覆包括气相包碳和/或固相包碳。
气相包碳的方法包括：将氧硅材料、掺杂氧硅材料或含有IA族元素的氧硅材料在保护性气氛下升温至600～1000℃，通入有机碳源气体，保温0.5～10h。
保护性气氛包括氮气气氛、氦气气氛、氖气气氛、氩气气氛、氪气气氛或氙气气氛中的至少一种。
有机碳源气体包括烃类；优选为甲烷、乙烯、乙炔或苯中的至少一种。
固相包碳的方法包括：将氧硅材料、掺杂氧硅材料或含有IA族元素的氧硅材料与碳源融合0.5h以上后，将得到的碳混合物在600～900℃下碳化2～6h。
上述融合在融合机中进行，融合机转速为500～3000r/min。
碳源包括聚合物、糖类、有机酸、沥青中的至少一种。
碳包覆的厚度为5～100nm；例如，可以为5nm、10nm、15nm、20nm、25nm、30nm、35nm、40nm、45nm、50nm、55nm、60nm、65nm、70nm、75nm、80nm、85nm、90nm、95nm、100nm或任意两个数值之间的任意一个数值。
当本申请的掺杂氧硅材料掺杂氧硅材料含有晶体硅，其他部分为非晶。
其制备方法包括：(1)将氧硅材料进行碳包覆，得到含有碳层的氧硅材料；(2)将IA族元素源和含有碳层的氧硅材料混合，进行第一次掺杂，得到第一次掺杂的氧硅材料；(3)将第一次掺杂的氧硅材料进行热处理后与非IA族元素源混合，进行第二次交换掺杂，得到所述掺杂氧硅材料。
碳包覆的条件为：温度850～1000℃，时间为0.5h～5h；可选地，在含有所述氧硅材料的装置中，通入碳源，气相沉积，得到含有碳层的氧硅材料。
碳包覆的温度可以为600℃、650℃、700℃、750℃、800℃、900℃、910℃、920℃、930℃、940℃、950℃、960℃、970℃、980℃、990℃、1000℃或任意两个数值之间的任意数值。
碳包覆时间可以为0.5h、0.6h、0.7h、0.8h、0.9h、1h、1.5h、2h、2.5h、3h、3.5h、4h、4.5h、5h、6h、7h、8h、9h、10h或任意两个数值之间的任意数值。
第一次掺杂的条件为：温度为5～40℃，时间为5～120h。
第一次掺杂的温度可以为5℃、6℃、7℃、8℃、9℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃或任意两个数值之间的任意数值。
第一次掺杂的时间可以为5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h、21h、22h、23h、24h、25h、26h、27h、28h、29h、30h、31h、32h、33h、34h、35h、36h、37h、38h、39h、40h、41h、42h、43h、44h、45h、46h、47h、48h、49h、50h、51h、52h、53h、54h、55h、56h、57h、58h、59h、60h、61h、62h、63h、64h、65h、66h、67h、68h、69h、70h、80h、90h、100h、110h、120h或任意两个数值之间的任意数值。
IA族元素源包括IA族元素的单质。
IA族元素源和氧硅材料的摩尔比为0.01～1:1。
IA族元素源和氧硅材料的摩尔比为0.01:1、0.02:1、0.03:1、0.04:1、0.05:1、0.06:1、0.07:1、0.08:1、0.09:1、0.1:1、0.2:1、0.3:1、0.4:1、0.5:1、0.6:1、0.7:1、0.8:1、0.9:1、1:1或任意两个比值之间的任意比值。
第一次掺杂为化学嵌入。
将IA族元素源和氧硅材料混合，放入溶液中，搅拌，得到第一次掺杂的氧硅材料。
溶液包括溶剂A和物质B；所述溶剂A包括四氢呋喃、1,2-二甲氧基乙烷、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚中的至少一种；所述物质B包括联苯及其衍生物，优选的，所述物质B为2-甲基联苯、4,4’-二甲基联苯中的至少一种。
第一次掺杂后的热处理的条件为：温度300～550℃，时间为1h～20h。例如温度可以为300℃、310℃、320℃、330℃、340℃、350℃、360℃、370℃、380℃、390℃、400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃或任意两个比值之间的任意比值；时间可以为1h、2h、3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h或任意两个数值之间的任意数值。
第一次掺杂后的热处理的条件为：温度400～550℃，时间为1h～10h。例如温度可以为400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃或任意两个比值之间的任意比值；时间可以为1h、2h、3h、4h、5h、6h、7h、8h、9h、10h或任意两个数值之间的任意数值。
第二次掺杂的条件为：温度为200～550℃，时间为4h～40h。
第二次掺杂的温度可以为200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃、290℃、300℃、310℃、320℃、330℃、340℃、350℃、360℃、370℃、380℃、390℃、400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃或任意两个比值之间的任意比值；时间可以为4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h、21h、22h、23h、24h、25h、26h、27h、28h、29h、30h、31h、32h、33h、34h、35h、36h、37h、38h、39h、40h或任意两个数值之间的任意数值。
非IA族元素源包括非IA族元素的氧化物、硫酸盐、卤化物中的至少一种，优选为非IA族元素的卤化物，卤化物由于不含有氧元素，对非IA族元素的吸引弱易解离，并且非IA族元素和A的硅酸盐中的硅酸根结合后能量更低，更稳定，反应温度降低。
第二次掺杂是通过离子交换的方式，将非IA族元素替代部分或全部IA族元素，克服了现有技术中，还原性较低的金属不能替代还原性较高金属的这一原料造成的遗憾；同时，与现有技术通过高温烧结的方式不同，该离子交换的方法条件温和，温度不高，不会使得材料中的硅和/或硅酸盐进行团聚而使得粒径增大；另外，该方法使处理过程中非IA族元素从表面向内部逐步取代IA族元素，对整个颗粒形成包裹，内部取代形成的包覆层与其他专利的整体包覆和颗粒表面包裹不同，该取代后的包裹层由于是金属元素的非晶化合物本身具备一定离子和电子电导，取代层可以很厚；其他专利的颗粒外部包裹则不同，其本身为晶体结构离子和电子导电性不强，因此不能太厚否则会影响材料电化学性能，其次本专利的内部取代包裹使得内部颗粒结合包覆紧密，结合力强，因此，即使经过搅拌等操作会造成一定的磨损，也使得其他微粒免受侵害。
非IA族元素源和第一次掺杂的氧硅材料的摩尔比为0.01～2:1。
非IA族元素源和第一次掺杂的氧硅材料的摩尔比为0.01:1、0.02:1、0.03:1、0.04:1、0.05:1、0.06:1、0.07:1、0.08:1、0.09:1、0.1:1、0.2:1、0.3:1、0.4:1、0.5:1、1:1、2:1或任意两个比值之间的任意比值。
由于在IA族元素的化合物中，处于外部的化合物易于被替代，所以非IA族元素是替代全部或部分IA族元素；当非IA族元素替代部分IA族元素时，随着反应的进行非IA族元素的化合物必然从颗粒表面逐步取代到颗粒内部，当非IA族元素替代全部IA族元素时，仅剩非IA族元素，那么非IA族元素的掺杂量就是全部金属元素的掺杂量。
该掺杂氧硅材料的制备方法在非氧化性气氛下进行。所述非氧化性气氛包括真空环境或惰性气氛；所述惰性气氛为氮气气氛、氦气气氛、氖气气氛、氩气气氛、氪气气氛或氙气气氛中的至少一种。
本申请通过先进行掺杂IA族元素，使其与氧硅材料中的氧进行结合，提前消耗锂，降低了在后续电池首次循环时对于锂或其他元素对于氧的结合，从而较大的提高了首效问题；接着，对于其中的IA族元素进行完全或部分替代，使其掺杂量降低，一方面可以降低其可以与水反应的量；同时，由于非IA族元素对 水的稳定性高，替代IA族元素最大程度上提升其与水的稳定性，保持材料结构稳定性，其次包覆为颗粒内部取代包覆层，具有致密度高，结合牢，相对于整体包覆，更具有实用性，即使受到磨损等操作使得整体结构破坏，也能对于每个IA族元素及其化合物进行针对性的保护。
掺杂氧硅材料为非晶材料时，即各个部分均为非晶。
其制备方法包括：(1)将A源与SiOz混合、搅拌，得到预嵌A的前驱体An·SiOz；(2)将预嵌A的前驱体An·SiOz在真空或惰性气体中加热；(3)将加热后的预嵌A的前驱体An·SiOz与M源混合，在真空或惰性气体氛围中进行烧结，得到所述掺杂氧硅材料。
步骤(3)烧结后，还包括洗涤过滤，具体为：将含有所述非晶电池材料的混合物在溶剂中洗涤过滤除去副产物。
在步骤(1)之前还包括：在SiOz表面进行气相碳沉积，得到碳包覆的SiOz。
步骤(1)中，在SiOz表面进行碳包覆的温度为700℃～800℃，时间为0.5～10h；
通过在SiOz表面进行气相碳沉积，使得SiOz表面获得碳包覆层，减少与电解质的接触面积，同时增加其导电性。在复合材料外表面存在碳包覆层，内部存在A和M，其中，碳包覆层包覆整个复合材料，不仅可以对复合材料起保护作用，还可以增加复合材料的导电性。
气相沉积是指将碳源气体在700～800℃沉积0.5～10h在SiOz表面。在700～800℃时，可以使得SiOz中Si的粒径不发生较大变化，尤其是不发生团聚而造成的颗粒粒径的增大；当Si粒径较大时，会影响后续该物质在电池中的循环性能。
沉积的温度可以为700℃、710℃、720℃、730℃、740℃、750℃、760℃、770℃、780℃、790℃、800℃或任意两个数值之间的任意数值。
沉积时间可以为0.5h、1h、1.5h、2h、2.5h、3h、3.5h、4h、4.5h、5h、5.5h、6h、6.5h、7h、7.5h、8h、8.5h、9h、9.5h、10h或任意两个数值之间的任意数值。
碳源气体的流速为1L/min～3L/min，例如可以为1L/min、1.5L/min、2L/min、2.5L/min、3L/min或任意两个数值之间的任意数值。
碳源气体包括天然气、甲烷、乙炔、丙烷、苯及甲苯中的至少一种。
气相沉积过程中还包括稀释气体；稀释气体用于降低碳源气体的含量，并且用于控制碳源气体沉积更加均匀。
所述稀释气体的流速为1L/min～3L/min，例如可以为1L/min、1.5L/min、2L/min、2.5L/min、3L/min或任意两个数值之间的任意数值。
所述稀释气体包括氩气、氮气、氖气、氦气、氪气、氙气中的至少一种。
步骤(1)是将A源与SiOz混合，放入溶液中，搅拌1～72h，过滤，即可得到预嵌A的前驱体An·SiOz。
所述A源与SiOz的质量比为(0.1～90)：100。进一步优选为(6～90)：100。
所述A源与SiOz的质量比为0.1：100、0.2：100、0.3：100、0.4：100、0.5：100、0.6：100、0.7：100、0.8：100、0.9：100、1：100、10：100、20：100、30：100、40：100、50：100、60：100、70：100、80：100、90：100或任意两个比值之间的任意一个比值。
A源为单质。
溶液包括溶剂A和物质B；所述溶剂A包括四氢呋喃、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚中的至少一种；所述物质B包括联苯及其衍生物。溶剂A优选为乙二醇二甲醚，物质B优选为2-甲基联苯，4,4’-二甲基联苯。
该过程在化学嵌入金属A的过程中，产生均为非晶的A的化合物，因而使得后续的离子交换过程中，M元素能够最大程度的替换锂锂或者钾元素，从而最大程度的减少负极活性物质颗粒中对水不稳定的硅酸锂/钾，以此提高负极活性物质颗粒对水的稳定性。
步骤(1)中，A源与SiOz混合、搅拌的温度为5℃～40℃，时间为1h～120h。
搅拌的温度可以为5℃、6℃、7℃、8℃、9℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃或任意两个数值之间的任意数值。
搅拌的时间可以为1h、2h、3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h、21h、22h、23h、24h、25h、26h、27h、28h、29h、30h、31h、32h、33h、34h、35h、36h、37h、38h、39h、40h、41h、42h、43h、44h、45h、46h、47h、48h、49h、50h、51h、52h、53h、54h、55h、56h、57h、58h、59h、60h、61h、62h、63h、64h、65h、66h、67h、68h、69h、70h、71h、72h、80h、85h、90h、95h、98h、100h、110h、120h或任意两个数值之间的任意数值。
步骤(1)得到的An·SiOz中，碱金属A分布于复合材料整个空间。
在步骤(3)中，M元素与A元素进行离子交换，完全替换或者部分替换材料中非晶的A的化合物。
由于M的还原性小于A的还原，使用一般的还原方法无法得到上述材料。本申请通过创新的离子交换的方法，使得目前还原性较低的金属替换金属A，让材料在预嵌A的过程中减少或者杜绝和氧结合的不可逆的金属A的消耗，因此提高了材料的首周循环效率。
所述M源与碳包覆的SiOz的质量比为(0.01～379)：100。
所述M源与碳包覆的SiOz的质量比为0.01:100、0.05:100、0.5:100、1:100、5:100、10:100、12：100、13：100、14：100、15：100、16：100、17：100、18：100、19：100、20：100、30：100、40：100、 50：100、60：100、70：100、80：100、90：100、100：100、110：100、120：100、130：100、140：100、150：100、160：100、170：100、180：100、190：100、200：100、300：100、379：100或任意两个比值之间的任意比值。
所述M源包括M的氧化物、卤化物、硫酸盐中的至少一种，优选为M的卤化物，卤化物由于不含有氧元素，对M离子吸引弱易解离，并且M元素和A的硅酸盐中的硅酸根结合后能量更低，更稳定，反应温度降低。
步骤(2)中，将预嵌A的前驱体An·SiOz在温度为300℃～500℃中加热1～6h。温度可以为300℃、350℃、400℃、350℃、500℃或任意两个数值之间的任意数值；时间可以为1h、2h、3h、4h、5h、6h或任意两个数值之间的任意数值。
因为化学嵌入金属A的过程，存在部分产物为金属A和硅的合金，该过程是将金属A和硅形成的合金中的金属A加速在在整个复合材料颗粒内部扩散，使其均匀分布；并且将其全部生成A的非晶化合物(A的硅酸盐或氧化物)，避免后续金属A和硅形成合金和M盐的副反应。并且进行加热处理后，碱金属A能够均匀的分布于复合材料的内部结构中。
步骤(3)中烧结温度为150℃～550℃，烧结时间为1～48h。
烧结温度可以为150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃、290℃、300℃、310℃、320℃、330℃、340℃、350℃、360℃、370℃、380℃、390℃、400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃或任意两个数值之间的任意数值；烧结时间可以为1h、2h、3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h、21h、22h、23h、24h、25h、26h、27h、28h、29h、30h、31h、32h、33h、34h、35h、36h、37h、38h、39h、40h、41h、42h、43h、44h、45h、46h、47h、48h或任意两个数值之间的任意数值。
该烧结过程中，发生离子交换，即金属M替代了金属A；该离子交换方法的条件温和，避免高温对于硅的影响，例如硅的聚集使得硅的粒径增大或使得硅让晶体硅转变；离子交换前后的A化合物和M化合物均为非晶，交换后M替代部分或全部A，让材料在预嵌A的过程中减少或者杜绝和氧结合的不可逆的A的消耗，因此可以提高材料的首周循环效率；并且离子交换不仅是表面交换同时存在体相交换，避免了仅仅表面包覆处理在后续的混料中可能存在颗粒碰撞导致的表面包覆破碎的问题，提高了浆料在混料过程中的稳定性。另外，该离子交换也避免了通过高温直接将金属M与SiOz中的能耗问题以及硅粒增大带来的各种影响，避免了纳米硅颗粒的团聚使得硅也保持着非晶状态。
该非晶电池材料的制备方法在非氧化性气氛下进行。所述非氧化性气氛包括真空环境或惰性气氛；所述惰性气氛为氮气气氛、氦气气氛、氖气气氛、氩气气氛、氪气气氛或氙气气氛中的至少一种。
目前制备硅负极材料中的一些问题，例如采用低温预锂氧化亚硅虽然保了预锂后材料中硅尺寸氧化硅中的硅颗粒尺寸小于1nm，优化参数后甚至能做到硅的颗粒更小，但是存在硅酸锂溶解导致浆料制备时残碱高的问题；以及采用二价金属元素虽然确保二价金属元素的硅酸盐，不会有溶于水的残碱问题，但是由于二价元素的金属或者氧化物和氧化硅反应的活性低，造成其和氧化硅反应温度高，导致合成材料中形成的硅的相的硅原子进行团聚长大，硅颗粒尺寸较大>20nm，造成制备材料循环和容量均下降的问题。而本实施例提供了一种非晶电池材料的制备方法，将调和上述两种方案的弊端，利用碱金属和氧化硅的高活性，采用低温预嵌的方案，从而确保预嵌金属后的硅保持不团聚的非晶状态，粒径小于1nm，将预嵌金属后形成的氧化亚硅与M源，在低温条件下进行离子交换反应，将硅酸盐中的锂部分或完全替换出来，减少碱金属的硅酸盐，从而确保了水中溶解的低残碱或者中性；并且M全部替代或部分替代A，生成对电解质更加稳定的M的硅酸盐，使得整个非晶电池材料的稳定性增强，且降低了在水中的碱性，提高了后续电池的使用寿命。
具体地，通过较低的温度对SiOz进行碳包覆，保持氧化亚硅的非晶特征；然后再用室温化学碱金属嵌入的方法向包碳的氧化亚硅中嵌入碱金属，在颗粒内部形成非晶的碱金属的硅酸盐化合物粒子；利用颗粒内部碱金属的硅酸盐化合物粒子结晶性较差从而具备一定的锂离子传导特性以及M和O结合能量降低，将M元素的卤化物与其进行混合加热进行离子交换，完全替换或者部分替换材料中非晶的碱金属的硅酸盐化合物，从而形成对水稳定的包覆结构，提高材料稳定性；反应后化学式：An-2y·My·SiOz；其中，0.7<z<1.2，0≤n-2y<z，0<y<0.5×z，由于是M取代部分A，M为二价元素，因此M的0<y<0.5×z；反应过后原子进行重组，由于采用离子交换法，温度不高、交换后的M化合物为非晶结构不影响纳米硅颗粒团聚使得硅也保持着非晶状态，因此提高了使用包含该负极活性物质颗粒的负极材料制备负极浆料时的稳定性以及使用该负极材料的二次电池的首周充放电效率和循环性能。
实施例3
根据本申请的又一方面，提供了一种负极材料，包括如上任一所述的掺杂氧硅材料。
掺杂氧硅在负极材料中的质量比例为≥2％。
掺杂氧硅还包括碳系材料。
碳系材料为人造石墨、天然石墨、软碳、硬碳、中间相炭微球(MCMB)中的至少一种；优选的，所述碳系材料为人造石墨和/或天然石墨。
实施例4
根据本申请的再一方面，提供了一种负极片，所述负极片包括如上任一所述的负极材料。
负极片还包括粘结剂、导电剂。
粘结剂包括丁苯橡胶(SBR)乳液、聚偏氟乙烯、羧甲基纤维素钠、羧甲基纤维素锂、聚丙烯酸、聚丙烯酸锂、聚丙烯酸钠的至少一种。
导电剂包括炭黑、导电石墨、碳纤维、碳纳米管、石墨烯中的至少一种。
根据本申请的再一方面，提供了一种电池，包括正极片、电解液、隔膜和如上任一所述的负极片。
实施例5
本实施例根据上述实施例的内容进行了具体的描述，设置了试验例和对比例，进行了相关的性能测试以及效果数据，具体如下：
该实施例中的掺杂氧硅材料含有晶体硅，其他部分为非晶。
掺杂量是掺杂元素与氧硅材料中的硅元素的摩尔比.
试验例1
(1)将3kg氧化亚硅(氧硅比0.91)，质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，940℃沉积2h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为2.4％。
(2)在氩气环境中，将IA族元素源(金属锂粒180g)、含碳层的氧化亚硅3kg，放入63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，在室温下(约25℃)搅拌110h进行化学嵌锂，然后将固液混合物进行过滤、干燥，得到掺杂IA族元素的硅酸盐化合物。
将得到的掺杂IA族元素的硅酸盐化合物放在管式炉中通入氮气升至500℃热处理3h后自然冷却，得到元素分布均匀的掺杂IA族元素的硅酸盐化合物。
取非IA族元素源(氯化钙1kg)与1kg掺杂IA族元素的硅酸盐化合物混合均匀，将混合物放在管式炉中通入氮气升至450℃烧结20h后自然冷却，后采用去离子水洗涤过滤除去杂质、干燥，得到掺杂氧硅材料；金属掺杂量为0.26，其中钙的掺杂量为0.10，锂的掺杂量为0.16。
图2为试验例1制备的掺杂氧硅材料的SEM图，从图中可以看出材料的粒径在6um左右，粒径大小比较均一；图3为试验例1制备的掺杂氧硅材料的能谱图，可以看出掺杂交换的钙元素与硅、氧元素分布的位置相差无几，这表明该氧硅材料中掺杂了钙元素；图4为试验例1制备的掺杂氧硅材料的XRD图，可以看出，该材料中只有晶体硅的特征峰，其他的硅酸盐的特征峰都不存在，这表明该材料中的硅酸盐都是非晶状态的，并且有X射线衍射图得知硅的晶体大小为4.6nm；图5为试验例1制备的掺杂氧硅材料的首周充放电曲线图，可以看出，该材料的首周充电容量为1478mAh/g，放电容量为1758mAh/g，首周效率为84.07％；图6为试验例1制备的掺杂氧硅材料的循环50周容量保持率图，可以看出该材料循环50周后的容量保持率为95.4％。
试验例2
(1)将3kg氧化亚硅(氧硅比0.91)，质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，930℃沉积2h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为2.5％。
(2)在氩气环境中，将IA族元素源(金属锂粒210g)、含碳层的氧化亚硅3kg，放入63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，在室温下(约25℃)搅拌100h进行化学嵌锂，然后将固液混合物进行过滤、干燥，得到掺杂IA族元素的硅酸盐化合物。
(3)将得到的掺杂IA族元素的硅酸盐化合物放在管式炉中通入氮气升至510℃热处理3h后自然冷却，得到元素分布均匀的掺杂IA族元素的硅酸盐化合物。
(4)取非IA族元素源(氯化镁1kg)与1kg掺杂IA族元素的硅酸盐化合物混合均匀，将混合物放在管式炉中通入氮气升至380℃烧结26h后自然冷却，后采用去离子水洗涤过滤除去杂质、干燥，得到掺杂氧硅材料；金属掺杂量为0.27，其中镁的掺杂量为0.15，锂的掺杂量为0.12。
试验例3
(1)将3kg氧化亚硅(氧硅比0.82)，质置于CVD回转炉中，以2L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，890℃沉积2h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为3.2％。
(2)在氩气环境中，将IA族元素源(金属锂粒180g)、含碳层的氧化亚硅3kg，放入63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，在室温下(约25℃)搅拌90h进行化学嵌锂，然后将固液混合物进行过滤、干燥，得到掺杂IA族元素的硅酸盐化合物。
(3)将得到的掺杂IA族元素的硅酸盐化合物放在管式炉中通入氮气升至490℃热处理3h后自然冷却，得到元素分布均匀的掺杂IA族元素的硅酸盐化合物。
(4)取非IA族元素源(氯化镁0.2kg)与1kg掺杂IA族元素的硅酸盐化合物混合均匀，将混合物放在管式炉中通入氮气升至400℃烧结16h后自然冷却，后采用去离子水洗涤过滤除去杂质、干燥，得到掺杂氧硅材料；金属掺杂量为0.28，其中镁的掺杂量为0.02，锂的掺杂量为0.31。
试验例4
(1)将3kg氧化亚硅(氧硅比1.01)，质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，900℃沉积3h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为3.6％。
(2)在氩气环境中，将IA族元素源(金属锂粒300g)、含碳层的氧化亚硅3kg，放入63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，在室温下(约25℃)搅拌110h进行化学嵌锂，然后将固液混合物进行过滤、干燥，得到掺杂IA族元素的硅酸盐化合物。
(3)将得到的掺杂IA族元素的硅酸盐化合物放在管式炉中通入氮气升至480℃热处理3h后自然冷却，得到元素分布均匀的掺杂IA族元素的硅酸盐化合物。
(4)取非IA族元素源(氯化镁2kg)与1kg掺杂IA族元素的硅酸盐化合物混合均匀，将混合物放在管式炉中通入氮气升至300℃烧结36h后自然冷却，后采用去离子水洗涤过滤除去杂质、干燥，得到掺杂氧硅材料；金属掺杂量为0.44，其中镁的掺杂量为0.19，锂的掺杂量为0.25。
试验例5
(1)将3kg氧化亚硅(氧硅比0.91)，质置于CVD回转炉中，以1.8L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，960℃沉积2h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为2.88％。
(2)在氩气环境中，将IA族元素源(锂粒120g)、含碳层的氧化亚硅3kg，放入63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，在室温下(约25℃)搅拌80h进行化学嵌锂，然后将固液混合物进行过滤、干燥，得到掺杂IA族元素的硅酸盐化合物。
(3)将得到的掺杂IA族元素的硅酸盐化合物放在管式炉中通入氮气升至520℃热处理3h后自然冷却，得到元素分布均匀的掺杂IA族元素的硅酸盐化合物。
(4)取非IA族元素源(氯化镁1kg)与1kg掺杂IA族元素的硅酸盐化合物混合均匀，将混合物放在管式炉中通入氮气升至280℃烧结30h后自然冷却，后采用去离子水洗涤过滤除去杂质、干燥，得到掺杂氧硅材料；金属掺杂量为0.16，其中镁的掺杂量为0.08，锂的掺杂量为0.08。
试验例6
(1)将3kg氧化亚硅(氧硅比0.91)，质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，920℃沉积2h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为2.4％。
(2)在氩气环境中，将IA族元素源(钾粒900g)、含碳层的氧化亚硅3kg，放入63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，在室温下(约25℃)搅拌120h进行化学嵌锂，然后将固液混合物进行过滤、干燥，得到掺杂IA族元素的硅酸盐化合物。
(3)将得到的掺杂IA族元素的硅酸盐化合物放在管式炉中通入氮气升至500℃热处理3h后自然冷却，得到元素分布均匀的掺杂IA族元素的硅酸盐化合物。
(4)取非IA族元素源(氯化镁1kg)与1kg掺杂IA族元素的硅酸盐化合物混合均匀，将混合物放在管式炉中通入氮气升至330℃烧结21h后自然冷却，后采用去离子水洗涤过滤除去杂质、干燥，得到掺杂氧硅材料；金属掺杂量为0.22，其中镁的掺杂量为0.10，钾的掺杂量为0.12。
试验例7
(1)将3kg氧化亚硅(氧硅比1.11)，质置于CVD回转炉中，以2L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，980℃沉积2.5h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为4.1％。
(2)在氩气环境中，将IA族元素源(金属锂粒60g)、含碳层的氧化亚硅3kg，放入63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，在室温下(约25℃)搅拌60h进行化学嵌锂，然后将固液混合物进行过滤、干燥，得到掺杂IA族元素的硅酸盐化合物。
(3)将得到的掺杂IA族元素的硅酸盐化合物放在管式炉中通入氮气升至530℃热处理3h后自然冷却，得到元素分布均匀的掺杂IA族元素的硅酸盐化合物。
(4)取非IA族元素源(氯化钙0.5kg)与1kg掺杂IA族元素的硅酸盐化合物混合均匀，将混合物放在管式炉中通入氮气升至450℃烧结26h后自然冷却，后采用去离子水洗涤过滤除去杂质、干燥，得到掺杂氧硅材料；金属掺杂量为0.08，其中钙的掺杂量为0.05，锂的掺杂量为0.03。
试验例8
(1)将3kg氧化亚硅(氧硅比0.91)，质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，870℃沉积3h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为3.6％。
(2)在氩气环境中，将IA族元素源(金属锂粒120g)、含碳层的氧化亚硅3kg，放入63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，在室温下(约25℃)搅拌80h进行化学嵌锂，然后将固液混合物进行过滤、干燥，得到掺杂IA族元素的硅酸盐化合物。
(3)将得到的掺杂IA族元素的硅酸盐化合物放在管式炉中通入氮气升至510℃热处理3h后自然冷却，得到元素分布均匀的掺杂IA族元素的硅酸盐化合物。
(4)取非IA族元素源(氯化锰1kg)与1kg掺杂IA族元素的硅酸盐化合物混合均匀，将混合物放在管式炉中通入氮气升至290℃烧结30h后自然冷却，后采用去离子水洗涤过滤除去杂质、干燥，得到掺杂氧硅材料；金属掺杂量为0.156，其中锰的掺杂量为0.086，锂的掺杂量为0.07。
试验例9
(1)将3kg氧化亚硅(氧硅比0.91)，质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，950℃沉积3h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为3.6％。
(2)在氩气环境中，将IA族元素源(金属锂粒90g)、含碳层的氧化亚硅3kg，放入63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，在室温下(约25℃)搅拌40h进行化学嵌锂，然后将固液混合物进行过滤、干燥，得到掺杂IA族元素的硅酸盐化合物。
(3)将得到的掺杂IA族元素的硅酸盐化合物放在管式炉中通入氮气升至520℃热处理3h后自然冷却，得到元素分布均匀的掺杂IA族元素的硅酸盐化合物。
(4)取非IA族元素源(氯化钙0.5kg和氯化镁0.5kg)与1kg掺杂IA族元素的硅酸盐化合物混合均匀，将混合物放在管式炉中通入氮气升至380℃烧结18h后自然冷却，后采用去离子水洗涤过滤除去杂质、干燥，得到掺杂氧硅材料；金属掺杂量为0.11，其中镁的掺杂量为0.04，钙的掺杂量为0.03，锂的掺杂量为0.04。
对比例1
(1)将3kg氧化亚硅(氧硅比0.91)，质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，940℃沉积2h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为2.4％。
(2)将质量相当于形成有碳层的氧化硅颗粒的4质量％的LiH粉末与该含碳层的氧化硅颗粒在氩气氛围下混合，并利用搅拌机进行了搅拌。然后，通过在氛围控制炉中对搅拌后的粉未进行740℃的热处理，从而将锂插入氧化硅颗粒中并进行了改性。
(3)将改性后的氧化硅颗粒投入乙醇与磷酸二氢铝的混合溶液中，进行搅拌、过滤、干燥并去除了乙醇。由此，使磷酸二氢铝附着于氧化硅颗粒的表面和碳层的表面。此时，改性后的氧化硅颗粒被磷酸二氢铝包覆。以此方式，制作了由在表面具有碳层和磷酸盐的覆膜的氧化硅颗粒构成的硅系活性物质颗粒。由X射线衍射图分析得知该硅系活性物质颗粒中的硅的晶体大小为6.63nm。
对比例2
(1)将3kg氧化亚硅(氧硅比0.91)，质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，940℃沉积2h，冷却出料得到含碳层的氧化亚硅。该碳层在所述掺杂氧硅材料中的质量分数为2.4％。
(2)首先，将含碳层的氧化亚硅颗粒浸渍在使锂片与作为直链聚亚苯基化合物的联苯溶解于四氢呋喃(以下也称为THF)而得到的溶液(溶液A1)中。此时，将N2鼓泡至溶液A1中(以下述方式制作了溶液A1：以1mol/L的浓度使联苯溶解于THF溶剂中后，相对于该THF与联苯的混合液，添加6质量％的质量分率的锂片。此外，浸渍硅化合物颗粒时的溶液的温度为20℃，浸渍时间设为了10小时)。然后，过滤取得了硅化合物颗粒。通过以上处理，向硅化合物颗粒中插入了锂。接着，将插入锂后的硅化合物颗粒浸渍于使萘溶解于THF而得到的溶液(溶液B)中(以2mol/L的浓度将萘溶解于THF溶剂来制作了溶液B)。此外，浸渍硅化合物颗粒时的溶液的温度为20℃，浸渍时间设为了20小时。然后，过滤取得了硅化合物颗粒。
(3)将接触溶液B后的硅化合物颗粒浸渍于以1mol/L的浓度使对苯醌溶解于THF而得到的溶液(溶液C)中。浸渍时间设为了2小时。然后，过滤取得了硅化合物颗粒。接着，对硅化合物颗粒进行清洗处理，并在减压下对清洗处理后的硅化合物颗粒进行了干燥处理。以此方式得到了在表面包含氮化锂的负极活性物质颗粒。接着，用乙醇与水的混合溶液清洗该负极活性物质颗粒，由此在负极活性物质颗粒的表面生成了Li2CO3和LiOH。
对比例3
仅为试验例9中的前两个步骤，即对比例3得到的物质是试验例9步骤(3)中的掺杂IA族元素的硅酸盐化合物。
试验例10
将上述试验例1至试验例9以及对比例1-3制备的负极活性物质颗粒分别取10g，分别放入100mL的去离子水中，常温下以60r/min的转速搅拌10min，使用pH试纸测试(精密试纸)，用玻棒蘸一点待测溶液到试纸上，然后根据试纸的颜色变化并对照比色卡也可以得到溶液的pH值，结果见表1。
表1

如表1所示，比较对比例1与对比例3，可以发现两者制备最大的区别在于对比例1在嵌锂后利用磷酸二氢铝包覆对整体颗粒进行了包覆，从而使得对比例1比对比例3的pH值小碱性低；再比较试验例1、对比例1和对比例3，可以看出试验例1的pH值最小仅为7.6不仅低于对比例3的14，更低于对比例1的12.6，这表明本专利的材料在水中的稳定性要高于嵌锂后不进行处理的材料，也高于嵌锂后对颗粒整体进行包覆的材料。
再比较试验例1与对比例2，可以发现，对比例2的pH值为13.6远大于试验例1的7.6，这表明在嵌锂后的氧硅材料表面形成Li2CO3和LiOH的包覆层依旧会使得材料在水中显碱性，这其中包覆层虽然会起到一定阻止内部锂的硅酸盐的溶出，但材料表面的Li2CO3和LiOH在水中依旧会显碱性，相反，本发明的材料则是通过交换不仅形成对颗粒从外到内的包覆，更形成对颗粒内部锂的硅酸盐的体相包覆，从而可以确保材料在水中搅拌的稳定性。
试验例11
(1)将上述试验例1至试验例9以及对比例1-3制备的负极活性物质颗粒、SP、CNT、CMC和SBR按照75:12:3:5:5的质量比例进行浆料的制备，涂布在8μm的铜箔上，鼓风烘箱60℃干燥2h，然后裁取Ф12mm的极片若干装好放进真空烘箱110℃，干燥7h。
(2)待烘烤结束迅速转移至手套箱，以Ф14mm的金属锂片为对电极，使用单面陶瓷隔膜，以1mol/L的LiPF6/(EC+DMC)(体积比1:1)加3％的VC和3％FEC为电解液，在手套进行扣式电池组装，手套箱水氧含量控制在0.1ppm以下。
(3)对组装好的电池进行充放电循环测试，测试设备充放电测试在LAND电池测试系统(来源于武汉蓝合电子有限公司)上，测试条件为：室温，前三周按照0.1C、0.02C阶梯放电到5mV，0.1C恒流充电至1.5V，第四周后0.1C/0.1C充放电循环50周，结果见表2。(材料比容量计算方式为:充电的容量/负极活材料质量；电池首周效率计算方式为：电池首周充电比容量/电池首周放电比容量；电池50周容量保持率：将第50周的充电比容量/第一周的充电比容量)
表2实施例和对比例的掺杂氧硅材料的性能测试结果
如表2所示，比较试验例1至试验例9，可以发现氧硅材料的首效与第一次的嵌锂量(嵌锂量＝第一次嵌入的金属锂质量/参与反应的氧硅材料的质量)有关，在一定条件下，第一次的嵌锂量(嵌钾量可以根据摩尔质量换算成嵌锂量)越多则氧硅材料的首效则会越高；另外在一定条件下，第一次的嵌锂量越多则材料的可逆容量则会相对的降低；要说明的是，当第一次的嵌锂量较高时，即大于等于10％时，例如试验例4为10％时，材料的稳定性会有所下降从而导致首效有所降低，这表明本专利的材料在第一次的嵌锂量较低时，有比较大的优势。
而对于低嵌锂量(小于10％)时，则是嵌锂越多，首效越高。例如，比较试验例1与对比例1，可以看出，对比例1的第一次的嵌锂量较少故首效80.15％相比于试验例1的84.07％较少，但是与此同时可以看出，对比例1的可逆容量为1454mAh/g，也低于试验例1的可逆容量1478mAh/g，这表明对比例1由于包覆从而导致可逆容量降低；另外从50周容量保持率来看，对比例1的91.6％也低于试验例1的95.4％，这是由于对比例1的740℃高温热处理使得对比例1中的晶体硅的粒径变大为6.63nm大于试验例1的4.8nm，从而使得对比例1的循环性能差一些，并且由于对比例1是在嵌锂后的氧硅材料外利用磷酸盐进行包覆，对比例1的氧硅材料的包覆层很容易在负极浆料制备过程中破裂脱落，从而使得材料中的硅酸锂盐暴露出来从而使得循环性能下降。
比较对比例1、对比例2和试验例1，可以看出相较于试验例1，对比例2与对比例1有相同的痛点：1.额外的包覆层使得材料的容量降低；2.包覆层在制备负极浆料过程中容易破裂脱落使得材料中的硅酸锂盐暴露出来，从而在应用于电池时影响电池的循环性能。
比较试验例1与对比例2，两者第一次都嵌入了6％的金属锂，但是由于对比例2中的一部分锂变化形成了Li2CO3和LiOH，使得对比例2的首周效率为87.63％甚至低于试验例1的84.07％。
比较对比例3与试验例9，可以看出，两者都在第一次嵌入3％质量金属锂，但是对比例3的首效仅为73.35％，远不如试验例9的首效80.46％，对比例3的50周容量保持率为77.6％也远低于试验例9的95.6％，并且对比例3的材料在进行负极浆料制备时出现了部分团聚的现象，这表明了第一次嵌锂后不进行离子交换的材料容易在水中溶出锂的硅酸盐从而使得材料在水中不稳定，也使得其电池性能变差，其原因是不进行离子交换的对比例3由于缺少包覆层无法保护材料中的锂的硅酸盐部分，从而导致其在水中溶出，甚至可能会在该过程中生成二氧化硅，故对比例3的氧化亚硅嵌锂后不仅没有提升其首效甚至有所降低。
试验例12
(1)将上述实施例1至实施例3以及对比例制备的掺杂氧硅材料与石墨混合(质量比为10:90)得到混合负极材料，再将混合负极材料、SP、CNT、CMC和SBR按照95.4:0.3:0.5:1.6:2.2质量比例进行浆料的制备，涂布在8μm的铜箔上，鼓风烘箱60℃干燥2h，然后裁取Ф12mm的极片若干装好放进真空烘箱110℃，干燥7h。
(2)待烘烤结束迅速转移至手套箱，以Ф14mm的金属锂片为对电极，使用单面陶瓷隔膜，以1mol/L的LiPF6/(EC+DMC)(体积比1:1)加3％的VC和3％FEC为电解液，在手套进行扣式电池组装，手套箱水氧含量控制在0.1ppm以下。
(3)对组装好的电池进行充放电循环测试，测试设备充放电测试在武汉蓝合电子有限公司LAND电池测试系统上，测试条件为：室温，前三周按照0.1C、0.02C阶梯放电到5mV，0.1C恒流充电至1.5V，第四周后0.1C/0.1C充放电循环40周，结果见表3。(材料比容量计算方式为:充电的容量/负极活性物质质量；电池首周效率计算方式为：电池首周充电比容量/电池首周放电比容量；电池40周容量保持率：将第40周的充电比容量/第一周的充电比容量)
表3实施例和对比例与石墨混合的负极材料的性能测试结果
如表3所示，从40周容量保持率来看，可以发现对比例1-3都低于试验例1-9，并且其中对比例3的最低仅为93.7％，这表明嵌锂后的氧硅材料不进行包覆的话裸露的硅酸锂盐会影响材料的循环性能，而对比例1-2的保持率也低于试验例的原因是对比例1-2的包覆层都是表面包覆层，其容易在负极浆料制备过程中的因搅拌碰撞而破裂脱落使得材料中的硅酸锂盐暴露出来，从而影响了循环性能。
实施例6
掺杂氧硅材料为非晶材料时，即各个部分均为非晶。
试验例1
(1)将3kg氧化亚硅(SiOz，0.7<z<1.2)置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，以1.5L/min的流量通入氩气作为稀释气，800℃沉积4h，冷却出料得到具有一定碳包覆量(0.1％～10％)的氧化亚硅。
(2)在氩气环境中，将碱金属颗粒A、碳包覆的氧化亚硅3kg，放入63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，室温下(约25℃)搅拌120h进行化学嵌锂，然后将固液混合物进行过滤，得到含锂的氧化亚硅。
(3)采用加热方式，将步骤(2)中的嵌锂的氧化亚硅在500℃真空加热3h，使得嵌入的锂分布均匀，形成均匀的锂的硅酸盐；之后取M源与1kg加热后的嵌锂的氧化亚硅混合均匀，将混合物放在管式炉中通入氮气280℃烧结36h后自然冷却，用去离子水洗涤过滤除去氯化镁和氯化锂，干燥得到掺杂氧硅材料。
采用和上述步骤相似流程，仅仅更换其中的物质和实验参数，具体更换的实验参数见表4。表4
其中，试验例1～6中步骤(1)的乙炔的流量分别为1.5L/min、1.5L/min、2L/min、2.5L/min、1.5L/min、1.5L/min；碳包覆温度分别为800℃、800℃、800℃、800℃、760℃、700℃；碳包覆时间分别为4h、4h、3.5h、3h、4h、4h；试验例1～6中步骤(2)的室温下(约25℃)搅拌进行化学嵌锂的时间分别为120h、72h、120h、110h、60h、90h。
试验例1制备得到的掺杂氧硅材料的SEM图、元素能谱图和X射线衍射图如图8、图9和图10所示，具体地，如图8的SEM图所示，试验例1制备的非晶电池材料的粒径在5μm左右；如图9所示的EDS能谱图可以看出，试验例1制备的非晶电池材料中外部有碳元素包覆，材料内部除了含有本身的硅、氧元素之外还含有镁元素，这表明镁元素通过离子交换成功地替换了锂元素进入了材料内部，而且镁元素在材料的颗粒内部分布的较为均匀，这说明了非晶的锂的硅酸盐能够最大程度地进行离子交换。如图10所示，试验例1的的XRD图中没有明显的特征峰，只存在两个非晶的鼓包曲线，即在衍射角14°<2θ<40°存在一个非晶鼓包曲线且设鼓包曲线面积为S1，在衍射角40°<2θ<60°存在一个非晶鼓包曲线且设鼓包曲线面积为S2，0<S2/S1<1。
对比例1
将3kg氧化亚硅(SiOz，z＝0.91)置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，以1.5L/min的流量通入氩气作为稀释气，800℃沉积4h，冷却出料得到碳包覆的氧化亚硅，碳包覆量为3.6％。即，仅为试验例1中步骤(1)得到的物质。
对比例2
(1)将3kg氧化亚硅(SiOz，z＝0.91)置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，以1.5L/min的流量通入氩气作为稀释气，800℃沉积4h，冷却出料得到碳包覆的氧化亚硅，碳包覆量为3.6％。(2)在氩气环境中，将碱金属颗粒A(锂粒90g)、碳包覆的氧化亚硅3kg，放入63g4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，搅拌120h进行化学嵌锂，然后将固液混合物进行过滤，得到嵌锂的氧化亚硅。(3)采用加热方式，将步骤(2)中的嵌锂的氧化亚硅在500℃真空加热3h，使得嵌入的锂分布均匀，形成均匀的锂的硅酸盐，得到均匀嵌锂的氧化亚硅，即，仅为试验例2中步骤(1)和步骤(2)和热处理，不进行离子交换得到的物质。
对比例3
(1)在0.0001～1torr的减压气氛下以1400℃的温度热处理15kg的以1：1的摩尔比均匀混合硅粉末与二氧化硅(SiO2)粉末的粉末和1.5kg的镁，使上述硅、二氧化硅(SiO2)的混合粉末的氧化硅蒸汽与镁蒸汽同时产生来气相中进行反应后，在700℃的温度下进行冷却后析出，随后用气流粉碎机进行粉碎并分级，从而获得包含平均粒径(D50)为6.3μm的镁的氧化硅复合物粉末。(2)按照与对比例1相同的方法，对步骤(1)中的掺杂氧硅材料进行包覆，得到电池材料。
性能测试
1、pH值
将上述试验例1～6以及对比例1～3制备的含锂的氧化亚硅分别取10g，分别放入100mL的去离子水中，常温下以60r/min的转速搅拌10min，使用pH计测试分别测试pH值，结果见表5。
表5

如表5所示，通过对比例1、对比例2与对比例3可以看出，对比例2的pH值为13.6远大于对比例1的7.0，表明氧化亚硅嵌锂后的材料在水中显较强的碱性；对比例3与对比例1的pH相差无几都是接近中性，表明氧化亚硅嵌入镁不会影响材料在水中的pH值；通过试验例1-6与对比例2的数据，试验例1～6的pH值都在7～9之间远小于对比例2的13.6，这表明本发明通过离子交换可以有效的降低嵌锂的氧化亚硅在水中的碱性。
2、电学性能
(1)将上述试验例1～6以及对比例1～3制备的掺杂氧硅材料、SP、CNT、CMC和SBR按照75:12:3:5:5的质量比例进行浆料的制备，涂布在8μm的铜箔上，鼓风烘箱60℃干燥2h，然后裁取Ф12mm的极片若干装好放进真空烘箱110℃，干燥7h。
(2)待烘烤结束迅速转移至手套箱，以Ф14mm的金属锂片为对电极，使用单面陶瓷隔膜，以1mol/L的LiPF6/(EC+DMC)(体积比1:1)加3％的VC和3％FEC为电解液，在手套进行扣式电池组装，手套箱水氧含量控制在0.1ppm以下。
(3)对组装好的电池进行充放电循环测试，测试设备充放电测试在LAND电池测试系统(来源于武汉蓝合电子有限公司)上，测试条件为：室温，前三周按照0.1C、0.02C阶梯放电到5mV，0.1C恒流充电至1.5V，第四周后0.1C/0.1C充放电循环50周，结果见表6。(材料比容量计算方式为:充电的容量/掺杂氧硅材料质量；电池首周效率计算方式为：电池首周充电比容量/电池首周放电比容量；电池50周容量保持率：将第50周的充电比容量/第一周的充电比容量)
表6实施例和对比例的掺杂氧硅材料的性能测试结果
图11和图12分别是试验例1的首次充放电曲线和50周容量保持率图，通过图11可以看出，试验例1的首次充电容量为1475mAh/g，首次放电容量为1728mAh/g；通过图12可以看到，除了刚开始的八次循环上下浮动较大外，之后均无明显波动，且在循环50次之后，处于较稳定状态，可见本申请试验例1制备的非晶材料具有较高的50周容量保持率，且循环过程均处于稳定状态。
如表6所示，通过验例1与对比例1可以看出，试验例1的首周效率为85.33％远大于对比例1的75.25％，且试验例1的50周容量保持率为96.7％同样远大于对比例1的81.6％，这表明本发明通过嵌锂然后进行离子交换的硅氧材料可以提升氧化亚硅的首效与循环性能。
通过试验例2与对比例2可以看出，对比例2与试验例2的制备的不同之处仅在于对比例2进行了嵌锂后没有进行离子交换，然而对比例2的充放电容量都远低于试验例2，并且对比例2的首效仅为73.31％也远低于试验例2的81.75％(需要补充的是，对比例2在制备浆料时出现了团聚现象)，此外对比例2的50周循环保持率只有76.6％远低于试验例2的96.3％，这表明试验例2由于离子交换用镁元素替换了锂元素，相较于嵌锂后不进行离子交换的氧化亚硅材料，提高了材料的稳定性和循环性能。
比较试验例2与对比例3可以看出，对比例3没有进行嵌锂而是直接高温将镁嵌入了硅氧材料，而镁元素的相对原子质量为24，锂元素的相对原子质量为7，通过换算对比例3的嵌镁量(嵌镁量＝嵌入镁元素质量/氧化亚硅质量)10％换算成嵌锂量(嵌锂量＝嵌入锂元素质量/氧化亚硅质量)为2.9％(即10％/24*7≈2.9％)，与试验例2的嵌锂量3％接近，故对比例3的首效为81.41％略低于试验例2的81.75％，相差不多；而对比例3的50周循环保持率仅为85％远低于试验例2的96.3％，这表明对比例3由于高温嵌镁导致硅氧材料中的晶体硅的粒径变大，从而导致了材料的循环性能变差。
3、与石墨混合后的电学性能
(1)将上述实施例1至实施例3以及对比例制备的掺杂氧硅材料与石墨混合(质量比为10:90)得到混合负极材料，再将混合负极材料、SP、CNT、CMC和SBR按照95.4:0.3:0.5:1.6:2.2质量比例进行浆料的制备，涂布在8μm的铜箔上，鼓风烘箱60℃干燥2h，然后裁取Ф12mm的极片若干装好放进真空烘箱110℃，干燥7h。
(2)待烘烤结束迅速转移至手套箱，以Ф14mm的金属锂片为对电极，使用单面陶瓷隔膜，以1mol/L的LiPF6/(EC+DMC)(体积比1:1)加3％的VC和3％FEC为电解液，在手套进行扣式电池组装，手套箱水氧含量控制在0.1ppm以下。
(3)对组装好的电池进行充放电循环测试，测试设备充放电测试在武汉蓝合电子有限公司LAND电池测试系统上，测试条件为：室温，前三周按照0.1C、0.02C阶梯放电到5mV，0.1C恒流充电至1.5V，第四周后0.1C/0.1C充放电循环50周，结果见表7。(材料比容量计算方式为:充电的容量/掺杂氧硅材料质量；电池首周效率计算方式为：电池首周充电比容量/电池首周放电比容量；电池50周容量保持率：将第50周的充电比容量/第一周的充电比容量)
表7实施例和对比例的掺杂氧硅材料与石墨混合的负极材料的性能测试结果
如表7所示，通过比较试验例1与对比例1，可以看出对比例1的首效为86.05％低于试验例1的91.14％，且对比例1的50周容量保持率为93.6％也低于试验例1的99.1％，这表明本发明嵌锂并进行离子交换的硅氧材料相较于单纯的碳包覆氧化亚硅应用于负极材料中时，会提高材料的首效与循环性能。通过比较试验例2与对比例2，可以看出对比例2的充放电容量、首效以及50周容量保持率都明显低于试验例2，这表明单纯预锂后的材料如果不进行表面包覆或者如本专利的离子交换进行体相包覆，则在应用于负极材料时会极大影响电池的电化学性能。
通过比较试验例1与对比例3，可以看出两者的首效相差无几，这是因为两者在进行嵌锂与嵌镁时结合硅氧材料中的氧元素差不多，故两者应用于负极材料时的首效相差无几；然而对比例3的50周容量保持率为95.4％低于试验例1的99.1％，这表明高温嵌镁导致对比例3的硅氧材料中的晶体硅粒径变大，而试验例1是采用低温嵌锂以及较低温度进行的离子交换使得硅氧材料中的硅为非晶状态，粒径小于1nm，因此试验例1应用于负极材料时的循环性能要优于对比例3应用于负极材料的循环性能。
实施例7
根据本申请的内容，对实施例1的制备方法进行了具体说明，具体描述如下所示：
试验例1
将5kg氧化亚硅(SiOx，其中，x＝0.9)，质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，940℃沉积2h，冷却出料得到碳包覆的氧化亚硅并进行分筛。
在氩气气氛中，将180g金属锂粒溶解于63g 4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，再将3kg筛分后碳包覆的氧化亚硅浸渍于上述溶液中，室温下(约25℃)搅拌110h进行化学嵌锂，然后将固液混合物进行过滤，得到碳包覆的嵌锂的氧化亚硅，将其干燥。
将得到的碳包覆的嵌锂的氧化亚硅在氩气环境中500℃热处理3h。
取1kg氯化钙与1kg碳包覆嵌锂的氧化亚硅高速混合均匀，将混合物放在管式炉中通入氮气升温至450℃烧结20h后自然冷却，再采用去离子水洗涤过滤除去氯化钙和氯化锂，干燥得到嵌锂和掺钙的掺杂氧硅材料。
图13为试验例1制备的掺杂氧硅材料的SEM图，从图中可以看出材料的粒径在6um左右，粒径大小比较均一；图14为试验例1制备的第一次嵌锂后与第二次离子交换后的氧硅材料的ICP图，可以看出第一次嵌锂后的硅基材料中并没有钙元素(ICP无法测试出锂的含量)，而第二次离子交换后的氧硅材料中则有钙元素，这表明该氧硅材料通过嵌锂然后离子交换确实掺杂了钙元素；图15为试验例1制备的掺杂氧硅材料的XRD图，通过该图可知，该材料中只有晶体硅的特征峰，其他的硅酸盐的特征峰都不存在，这表明该材料中的硅酸盐都是非晶状态的，并且有X射线衍射图得知硅的晶体大小为4.6nm；图16为 试验例1制备的掺杂氧硅材料的首周充放电曲线图，可以看出，该材料的首周充电容量为1470mAh/g，放电容量为1740mAh/g，首周效率为84.48％；图17为试验例1制备的掺杂氧硅材料的循环50周容量保持率图，可以看出该材料循环50周后的容量保持率为95.2％。
试验例2
将3kg氧化亚硅(SiOx，其中，x＝0.91)，质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，920℃沉积3h，冷却出料得到含碳层的氧化亚硅。
在氩气环境中，将300g金属锂粒溶解于63g4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，再将3kg氧化亚硅(SiOx，其中，x＝1.1)浸渍于上述溶液中，室温下(约25℃)搅拌72h进行化学嵌锂，然后将固液混合物进行过滤，得到碳包覆的嵌锂的氧化亚硅，将其干燥。
将得到的嵌锂的氧化亚硅在氩气环境中680℃热处理3h。
取0.15kg氯化镁与1kg嵌锂的氧化亚硅高速混合均匀，将混合物放在管式炉中通入氮气升温至435℃烧结10h后自然冷却，再采用去离子水洗涤过滤除去氯化镁和氯化锂，干燥得到嵌锂和掺镁的掺杂氧硅材料。
试验例3
将5kg氧化亚硅(SiOx，其中，x＝1.01)质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，800℃沉积3h，冷却出料得到碳包覆的氧化亚硅并进行分筛。
在氩气环境中，将120g金属锂粒放入63g4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，再将筛分后的碳包覆氧化亚硅3kg浸渍与上述溶液中，室温下(约25℃)搅拌72h进行化学嵌锂，然后将固液混合物进行过滤，得到碳包覆的嵌锂的氧化亚硅，将其干燥。
将得到的嵌锂的氧化亚硅在氩气环境中650℃热处理3h。
取1kg氯化镁与1kg碳包覆嵌锂的氧化亚硅高速混合均匀，将混合物放在管式炉中通入氮气升温至450℃烧结12h后自然冷却，再采用去离子水洗涤过滤除去氯化镁和氯化锂，干燥得到嵌锂和掺镁的掺杂氧硅材料。
试验例4
将5kg氧化亚硅(SiOx，其中，x＝1.01)，置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，800℃沉积4h，冷却出料得到碳包覆的氧化亚硅并进行分筛。
在氩气环境中，取1kg碳包覆的氧化亚硅、氢化锂80g置于高速分散机中，搅拌40min后取出置于气氛保护炉中在氩气气氛下进行高温烧结，温度600℃，时间5h，自然降温至室温取出碳包覆嵌锂的氧化亚硅。
取1kg氯化锰与1kg碳包覆嵌锂的氧化亚硅高速混合均匀，将混合物放在管式炉中通入氮气升温至350℃烧结15h后自然冷却，再采用去离子水洗涤过滤除去氯化锰和氯化锂，干燥得到嵌锂和掺锰的掺杂氧硅材料。
试验例5
在氩气环境中，将3kg氧化亚硅(SiOx，其中，x＝0.8)，与0.9kg氢化钾用三维混料机混合均匀后，然后在氩气保护下于720℃焙烧3h，得到嵌钾的氧化亚硅。
取3kg嵌钾的氧化亚硅颗粒质置于CVD回转炉中，以0.8L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，700℃沉积6h，冷却出料得到碳包覆嵌钾的氧化亚硅。
取1kg氯化钙与1kg碳包覆嵌钾的氧化亚硅高速混合均匀，将混合物放在管式炉中通入氮气升至450℃烧结3h后自然冷却，再采用去离子水洗涤过滤除去氯化钾和氯化钙，干燥得到嵌钾和掺杂钙的掺杂氧硅材料。
试验例6
将5kg氧化亚硅(SiOx，其中，x＝1.01)质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，800℃沉积3h，冷却出料得到碳包覆的氧化亚硅并进行分筛。
在氩气环境中，将90g金属锂粒放入63g4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，再将筛分后的碳包覆氧化亚硅3kg浸渍与上述溶液中，室温下(约25℃)搅拌72h进行电化学嵌锂，然后将固液混合物进行过滤，得到碳包覆的嵌锂的氧化亚硅，将其干燥。
将得到的嵌锂的氧化亚硅在氩气环境中520℃热处理3h。
取0.1kg氯化镁与1kg碳包覆嵌锂的氧化亚硅高速混合均匀，将混合物放在管式炉中通入氮气升温至500℃烧结9h后自然冷却，再采用去离子水洗涤过滤除去氯化镁和氯化锂，干燥得到嵌锂和掺镁的掺杂氧硅材料。
对比例1
与试验例6步骤大致相同，只是没有离子交换的步骤，具体如下：
将5kg氧化亚硅(SiOx，其中，x＝1.01)质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，800℃沉积3h，冷却出料得到碳包覆的氧化亚硅并进行分筛。
在氩气环境中，将90g金属锂粒放入63g4,4’-二甲基联苯与4L乙二醇二甲醚的混合溶液中，再将筛分后的碳包覆氧化亚硅3kg浸渍与上述溶液中，搅拌72h进行电化学嵌锂，然后将固液混合物进行过滤，得到碳包覆的嵌锂的氧化亚硅，将其干燥。
将得到的嵌锂的氧化亚硅在氩气环境中520℃热处理3h。，之后得到嵌锂的掺杂氧硅材料。
对比例2
取880g SiOx基复合材料(其是由无定形碳包覆层和市售SiOx(x＝1)形成的复合材料，且无定形碳占复合材料的3wt％)与120g Mg粉，即Mg占混合物的比例为12％，投入VC混合机内混合30min后，投入0.1MPa Ar气氛的箱式炉中于1000℃处理12h，使用HCl进行酸处理2h，然后过滤将酸液分离，然后将滤渣高温烘干，得到掺杂氧硅材料(还原SiOy材料和Mg的化合物)。
对比例3
在0.0001～1torr的减压气氛下以1400℃的温度热处理15kg的以1：1的摩尔比均匀混合硅粉末与二氧化硅(SiO2)粉末的粉末和1.5kg的镁，使上述硅、二氧化硅(SiO2)的混合粉末的氧化硅蒸汽与镁蒸汽同时产生来气相中进行反应后，在700℃的温度下进行冷却后析出，随后用气流粉碎机进行粉碎并分级，从而获得包含平均粒径(D50)为6.3μm的镁的氧化硅复合物粉末。
按照试验例6碳包覆的步骤碳包覆，即将所述粉碎的硅复合氧化物粉末质置于CVD回转炉中，以1.5L/min的流量通入乙炔作为碳源，通入氩气作为稀释气，800℃沉积3h，冷却出料得到碳包覆的嵌镁的氧化亚硅并进行分筛。
性能测试
将试验例和对比例1、对比例3制备的掺杂氧硅材料、SP、CMC和SBR按照75:15:5:5的质量比例进行浆料的制备，涂布在8μm的铜箔上，鼓风烘箱60℃干燥2h，然后裁取Ф12mm的极片若干装好放进真空烘箱110℃，7h进行干燥。
(2)待烘烤结束迅速转移至手套箱，以Ф14mm的金属锂片为对电极，使用单面陶瓷隔膜，以1mol/L的LiPF6/(EC+DMC)(体积比1:1)加3％的VC和3％FEC为电解液，在手套进行扣式电池组装，手套箱水氧含量控制在0.1ppm以下。
(3)对组装好的电池进行充放电循环测试，测试设备充放电测试在武汉蓝合电子有限公司LAND电池测试系统上，测试条件为：室温，前三周按照0.1C、0.02C阶梯放电到5mV，0.1C恒流充电至1.5V，第四周后0.1C/0.1C充放电循环40周(材料比容量计算方式为:充电的容量/负极活性物质质量；电池首周效率计算方式为：电池首周充电比容量/电池首周放电比容量)
表8试验例和对比例1、对比例3的掺杂氧硅材料的性能测试结果
如表8所示，比较试验例6与对比例1，两者第一次的嵌锂量(嵌锂量＝嵌入锂元素的质量/将要嵌锂的材料的质量)都为3％，差别仅在于嵌锂后是否进行离子交换，然而对比例1的首效仅为73.35％，远低于试验例6的81.54％，对比例1的50周容量保持率为77.6％也远低于试验例6的95.4％，并且对比例1的材料在进行负极浆料制备时出现了部分团聚的现象而试验例6未出现，这表明了第一次嵌锂后不进行离子交换的材料容易在水中溶出锂的硅酸盐从而使得材料在水中不稳定，也使得其电池性能变差；两者的性能测试比较可以看出本发明的材料在嵌锂后有进行离子交换可以有效的提升氧硅材料的首效与循环性能，并且由于离子交换形成的包覆能够提升材料的稳定性。
比较试验例3与对比例2：对比例2在880g SiOx基复合材料中嵌入120g镁，则嵌镁量为120/880约等于13.636％，换算成嵌锂量为13.636％/24*7约等于4％(镁的相对原子质量为24，锂的相对原子质量为7)，这与试验例3的嵌锂量4％(120/3000＝4％)相接近。通过比较两者的首周效率可以看出两者相差不大；然而对比例2的首次充电容量为1281mAh/g，首次放电容量为1541mAh/g，都远低于试验例3的1527mAh/g的首次充电容量和1834mAh/g的首次放电容量，这表明本专利先嵌锂然后通过离子交换嵌入镁元素的的材料容量相较于直接嵌镁会提升许多；其次对比例2的40周容量保持率为90.1％低于试验例3的97.6％，这表明对比例2由于1000℃的高温处理使得其材料中的晶体硅的粒径较大从而导致其循环性能较差。
比较试验例6与对比例3，通过计算两者的嵌锂量与嵌镁量，可以知道，对比例3的嵌镁量换算成嵌锂量为2.9％与试验例6的3％相接近，并且两者的首周效率分别为81.54％和81.41％，同样相差不多；然而对比例3的首周充放电容量都远低于试验例6，这表明直接高温嵌锂的方法制备的材料的容量较低，不如本发明的材料的容量；此外对比例3的50周容量保持率为85％也远低于试验例6的95.4％，这表明对比例3的高温将硅、二氧化硅、金属镁三者共同蒸镀冷却得到材料的方案会使材料的循环性较差，远不如本发明低温嵌锂后再以较低温离子交换嵌镁的方法制得的材料的循环性好，这是因为本发明的制备方案的低温制备可以保持材料中的硅不继续长大，从而使得材料的循环性能较好。
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内所作的任何修改、等同替换或改进等，均应包含在本申请的保护范围之内。

Claims (27)

  1. 一种掺杂氧硅材料，其特征在于，包括氧硅材料和掺杂于氧硅材料内的金属元素；
    所述金属元素以金属非晶化合物的形式存在于所述氧硅材料中；所述金属元素包括IUPAC(元素周期表)中的非IA族元素或非IA族元素与IA族元素的混合。
  2. 根据权利要求1所述的掺杂氧硅材料，其特征在于，所述金属元素的掺杂量为α，α的范围为：0<α≤1；所述非IA族元素的掺杂量为β，0<β≤α；所述IA族元素的掺杂量为(α-β)。
  3. 根据权利要求1所述的掺杂氧硅材料，其特征在于，在所述掺杂氧硅材料中，若同时掺杂IA族元素与非IA族元素，IA族元素位于掺杂氧硅材料中心区域，非IA族元素位于掺杂氧硅材料的外部区域；所述外部区域包覆所述中心区域；所述外部区域为中心区域至表面的中间区域。
  4. 根据权利要求1所述的掺杂氧硅材料，其特征在于，所述金属非晶化合物包括金属元素的氧化物和/或硅酸盐。
  5. 根据权利要求1所述的掺杂氧硅材料，其特征在于，所述非IA族元素包括IIA族元素、IIB族元素、VIIB族元素、VIII B族元素中的至少一种。
  6. 根据权利要求1所述的掺杂氧硅材料，其特征在于，所述IA族元素包括碱金属，优选为K和/或Li；
    所述IIA族元素包括Mg和/或Ca；所述IIB族元素包括Zn；所述VIIB族元素包括Mn；所述VIII B族元素包括Fe；
    优选地，所述非IA族元素包括二价金属和/或三价金属；
    优选地，所述金属元素包括K、Li、Mg、Ca、Mn、Fe和Zn中的至少一种。
  7. 根据权利要求1所述的掺杂氧硅材料，其特征在于，所述掺杂氧硅材料还含有晶体硅；所述掺杂氧硅材料的X射线衍射图谱包括衍射角26°<2θ<30°、46°<2θ<49°、54°<2θ<57°的特征峰；优选地，所述特征峰归属于晶体硅。
  8. 根据权利要求1所述的掺杂氧硅材料，其特征在于，所述掺杂氧硅材料的组成为An- 2y·My·SiOz；所述掺杂氧硅材料的主体结构为SiOz的非晶结构；
    其中，0.7<z<1.2，0≤n-2y<z，0＜n<z，0<y<0.5z；A为碱金属，M为二价金属；碱金属A的金属还原性大于二价金属M的金属还原性。
  9. 根据权利要求8所述的掺杂氧硅材料，其特征在于，当0<n-2y<z时，二价金属M的含量由掺杂氧硅材料表面至内部递减，碱金属A的含量由掺杂氧硅材料内部至表面递减。
  10. 根据权利要求8所述的掺杂氧硅材料，其特征在于，所述碱金属A包括锂和/或钾；二价金属M包括镁、钙、锰、锌、铁中的至少一种。
  11. 根据权利要求8所述的掺杂氧硅材料，其特征在于，所述碱金属A以A的非晶化合物存在于所述掺杂氧硅材料中；所述二价金属M以M的非晶化合物存在于所述掺杂氧硅材料中。
  12. 根据权利要求8所述的掺杂氧硅材料，其特征在于，所述A的非晶化合物包括A的硅酸盐和/或氧化物；所述M的非晶化合物包括M的硅酸盐和/或氧化物。
  13. 根据权利要求1～12任一所述的掺杂氧硅材料，其特征在于，所述掺杂氧硅材料还包括碳层；所述碳层包覆所述氧硅材料和所述金属元素。
  14. 根据权利要求13所述的掺杂氧硅材料，其特征在于，所述碳层的质量为掺杂氧硅材料质量的0.1％～10％。
  15. 一种根据权利要求1～14任一所述掺杂氧硅材料的制备方法，其特征在于，所述制备方法包括：(1)将氧硅材料与IA族元素源混合，进行碱金属元素的嵌入，得到含有IA族元素的氧硅材料；(2)将含有IA族元素的氧硅材料与非IA族元素源混合，进行离子交换，得到所述掺杂氧硅材料。
  16. 根据权利要求15所述的制备方法，其特征在于，所述硅基材料包括二氧化硅和/或氧化亚硅；所述IA族元素包括碱金属；所述IA族元素源包括IA族元素的单质、氢化物、硼氢化物、氨基化合物、烷基化合物；所述非IA族元素包括二价金属和/或三价金属；所述非IA族元素源包括非IA族元素的氧化物、硫酸盐、卤化物中的至少一种。
  17. 根据权利要求15所述的制备方法，其特征在于，所述氧硅材料与IA族元素源的质量比为1:(0.001～0.9)；所述非IA族元素源在含有IA族元素的硅基材料与非IA族元素源的质量之和的质量含量为0.01％～99％，优选为5％～67％。
  18. 根据权利要求15所述的制备方法，其特征在于，所述嵌入包括化学嵌入和/或高温烧结嵌入。
  19. 根据权利要求15所述的制备方法，其特征在于，所述化学嵌入包括：(1-1)将IA族元素源溶解于含有联苯及其衍生物的醚类溶液中，得到含IA族元素的溶液；(1-2)将氧硅材料浸渍于含IA族元素的溶液中，进行化学嵌入，得到所述含有IA族元素的氧硅材料；优选地，在步骤(1-2)之后还包括热处理；所述热处理是对含有IA族元素的氧硅材料进行加热；优选地，加热温度为300～750℃，加热时间为0.5～20h。
  20. 根据权利要求19所述的制备方法，其特征在于，所述化学嵌入的条件为：温度为5～40℃，时间为1～120h。
  21. 根据权利要求15所述的制备方法，其特征在于，所述高温烧结嵌入包括：将氧硅材料与IA族元素源混合，高温烧结，得到所述含有IA族元素的氧硅材料；优选地，所述高温烧结的温度为200～800℃，加热时间为1～20h。
  22. 根据权利要求15所述的制备方法，其特征在于，所述离子交换是指非IA族元素替代全部或部分IA族元素嵌入所述氧硅材料中，得到所述掺杂氧硅材料；优选地，所述离子交换的条件为：温度为150～650℃，时间为1～48h。
  23. 根据权利要求15所述的制备方法，其特征在于，所述制备方法还包括进行碳包覆；所述碳包覆可在步骤(1)之前、步骤(2)之后或步骤(1)与步骤(2)之间进行。
  24. 根据权利要求23所述的制备方法，其特征在于，所述碳包覆的条件为：温度600～1000℃，时间为0.5h～10h。
  25. 一种负极材料，其特征在于，包括权利要求1～14任一项所述的掺杂氧硅材料。
  26. 一种负极片，其特征在于，所述负极片包括权利要求25所述的负极材料。
  27. 一种电池，其特征在于，包括正极片、电解液、隔膜和权利要求26所述的负极片。
PCT/CN2023/091757 2022-05-07 2023-04-28 一种掺杂氧硅材料及其制备方法和应用 WO2023216940A1 (zh)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5395711A (en) * 1992-07-29 1995-03-07 Seiko Instruments Inc. Non-aqueous electrolyte secondary battery and its production method
CN109755500A (zh) * 2018-12-05 2019-05-14 华为技术有限公司 一种硅氧复合负极材料及其制作方法
CN111180692A (zh) * 2019-12-31 2020-05-19 安普瑞斯（南京）有限公司 一种用于电池的负极活性材料及其制备方法
CN112701267A (zh) * 2020-12-30 2021-04-23 湖州杉杉新能源科技有限公司 预锂化硅氧复合材料、负极极片、锂电池及其制备方法
WO2021136245A1 (zh) * 2019-12-31 2021-07-08 安普瑞斯（南京）有限公司 一种用于电池的负极活性材料及其制备方法
CN113948692A (zh) * 2021-12-20 2022-01-18 常州硅源新能材料有限公司 一种用于锂离子二次电池的含有惰性涂层包覆的硅氧化物复合材料及其制备
CN115719799A (zh) * 2022-05-07 2023-02-28 四川物科金硅新材料科技有限责任公司 一种非晶电池材料及其制备方法和应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5395711A (en) * 1992-07-29 1995-03-07 Seiko Instruments Inc. Non-aqueous electrolyte secondary battery and its production method
CN109755500A (zh) * 2018-12-05 2019-05-14 华为技术有限公司 一种硅氧复合负极材料及其制作方法
CN111180692A (zh) * 2019-12-31 2020-05-19 安普瑞斯（南京）有限公司 一种用于电池的负极活性材料及其制备方法
WO2021136245A1 (zh) * 2019-12-31 2021-07-08 安普瑞斯（南京）有限公司 一种用于电池的负极活性材料及其制备方法
CN112701267A (zh) * 2020-12-30 2021-04-23 湖州杉杉新能源科技有限公司 预锂化硅氧复合材料、负极极片、锂电池及其制备方法
CN113948692A (zh) * 2021-12-20 2022-01-18 常州硅源新能材料有限公司 一种用于锂离子二次电池的含有惰性涂层包覆的硅氧化物复合材料及其制备
CN115719799A (zh) * 2022-05-07 2023-02-28 四川物科金硅新材料科技有限责任公司 一种非晶电池材料及其制备方法和应用

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