CN106356508B - Composite, preparation method thereof, and negative electrode and lithium ion battery prepared from composite - Google Patents
Composite, preparation method thereof, and negative electrode and lithium ion battery prepared from composite Download PDFInfo
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- CN106356508B CN106356508B CN201610863902.7A CN201610863902A CN106356508B CN 106356508 B CN106356508 B CN 106356508B CN 201610863902 A CN201610863902 A CN 201610863902A CN 106356508 B CN106356508 B CN 106356508B
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- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to a compound, a preparation method thereof, and a negative electrode and a lithium ion battery prepared from the compound. The compound comprises silicon and silicon oxide SiOx(0<x is less than or equal to 2) and silicate, wherein the cation element of the silicate is a reducing agent element, and Si, O and the reducing agent element in the compound are uniformly distributed. The invention uses a reducing agent to heat and preserve heat in a negative pressure environment, so that SiO steam and the reducing agent steam react in a gas phase form and are condensed to obtain a compound, and the compound is further used as a raw material to prepare the modified silicon-oxygen cathode material. The negative electrode material is very suitable for a lithium ion battery, and the prepared lithium ion battery has high charge-discharge specific capacity and excellent first coulombic efficiency, the charge capacity is more than 1447mAh/g, the discharge capacity is more than 1213mAh/g, and the first coulombic efficiency is more than 83.8%.
Description
Technical Field
The invention belongs to the field of energy storage materials and electrochemistry, and relates to a compound, a preparation method thereof, and a negative electrode and a lithium ion battery prepared by the compound.
Background
With the increasing requirements of electronic products such as mobile phones, notebooks, digital cameras, micro video cameras and the like on energy supply equipment, especially the rapid development of power vehicles such as electric automobiles and the like, the development of novel green high-energy chemical power sources is particularly urgent. The lithium ion battery has the advantages of high specific capacity, high charging and discharging efficiency, good cycle performance and low cost, and thus becomes a hotspot of research work. The cathode material is used as an important component of the lithium ion battery, affects the specific energy and the cycle life of the lithium ion battery, and is always the focus of the research on the lithium ion battery.
However, the silicon material has large volume expansion rate (more than 300 percent) and low conductivity, so that the commercial application of the silicon material is limited, the theoretical capacity of SiO is lower than that of silicon, but the strength of Si-O bond is twice that of Si-Si bond, and L i generated in the first-week reaction process is L i2The O compound has a buffering effect on volume expansion, so that the cycle performance is much superior to that of silicon, but the excess L i is excessive2O increases the consumption of L i ions in the positive electrode material during the first charge, thereby increasing the irreversible capacity of the material and reducing the first coulombic efficiency.
CN 105789590 a discloses a preparation method of a SIOx/C negative electrode material, comprising the following steps: (1) carrying out heat treatment on the silica fume with the average particle size of 1-20 microns at 800-1100 ℃ for 1-10 hours under the protection of argon, and cooling to room temperature along with the furnace; (2) uniformly mixing the silica powder treated in the step (1) with an organic carbon source according to a mass ratio of 1: 1-10: 1, adding deionized water or absolute ethyl alcohol which is 0.5-5 times of the weight of the solid mixture, and grinding the mixture for 0.5-6 hours to obtain uniformly dispersed nano slurry; (3) carrying out spray drying on the nano slurry obtained in the step (2), wherein the inlet temperature of the spray drying is 200-350 ℃, and the outlet temperature of the spray drying is 90-150 ℃, so as to obtain a spherical particle precursor; (4) and (4) roasting the precursor obtained in the step (3) for 2-12 hours at 500-900 ℃ in a nitrogen or argon protective atmosphere, cooling to room temperature, and then crushing and sieving to obtain the SiOx/C composite negative electrode material. The SiOx/C composite negative electrode material prepared has the advantages of high first charge efficiency, good cycle performance and the like, and is suitable for being used as a negative electrode material of a lithium ion battery. However, the first charge-discharge efficiency is below 77%, which is still relatively low, and thus cannot meet the requirements of practical application.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a composite, a method for preparing the same, and a negative electrode and a lithium ion battery prepared from the composite. The distribution of each element (Si and O elements or Si, O and silicate cation elements) in the composite is uniform, the modified silica negative electrode material prepared by adopting the composite as a raw material is very suitable for a lithium ion battery, the prepared lithium ion battery has higher charge-discharge specific capacity and excellent first coulombic efficiency, the charge capacity is more than 1447mAh/g, the discharge capacity is more than 1213mAh/g, and the first coulombic efficiency is more than 83.8 percent, and the preparation methods of the composite and the negative electrode material are simple and feasible, are easy to implement industrially and have important potential application prospects.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a composite comprising silicon, silicon oxide and silicate, wherein the cation element in the silicate is a reducing agent element, and the Si, O and the reducing agent element are uniformly distributed, wherein the chemical composition of the silicon oxide is SiOx，0<x≤2。
Preferably, the silicate in the compound of the present invention may be, for example, lithium silicate, sodium silicate, magnesium silicate, aluminum silicate, calcium silicate, zinc silicate, iron silicate, or the like, and the cation element of the corresponding silicate is a reducing agent element, which is L i element, Na element, Mg element, Al element, Ca element, Zn element, Fe element, or the like, respectively.
For example, when the silicate in the compound is magnesium silicate, the corresponding reducing agent element is Mg element, and Si, O and Mg elements in the compound are uniformly distributed. Further, for example, when the silicate in the compound is a mixture of magnesium silicate and aluminum silicate, Si, O, Mg and Al elements in the compound are uniformly distributed.
Preferably, the compound also comprises a reducing agent and/or an oxide of the reducing agent, and Si, O and the reducing agent element in the compound are uniformly distributed, and the reducing agent element is derived from the silicate and the reducing agent and/or the oxide of the reducing agent.
The "reducing agent and/or oxide of the reducing agent" in the present invention means: is a reducing agent, or is an oxide of a reducing agent, or is a mixture of a reducing agent and an oxide of a reducing agent. In all three cases, the reducing agent may be a single kind of reducing agent, a single kind of reducing agent oxide, or a mixture of non-single kinds.
Preferably, the reducing agent is L i, any one or a mixture of at least two of Na, Mg, Al, Ca, Zn or Fe, and the corresponding reducing agent element is L i, any one or a combination of at least two of Na, Mg, Al, Ca, Zn or Fe.
Preferably, the oxide of the reducing agent is L i, any one of Na, Mg, Al, Ca, Zn or Fe or a mixture of at least two reducing agent oxides, such as L i2O，Na2O，MgO，Al2O3，CaO，ZnO，Fe2O3，Li2O and Na2Mixtures of O, L i2Mixture of O and MgO, Al2O3And Fe2O3Mixture of (A) and (B), Na2O, CaO and ZnO.
For example, when the compound further comprises an oxide L i of a reducing agent2O and a reducing agent L i, wherein the elements of Si, O and L i in the compound are uniformly distributed, wherein the L i element comes from three parts, namely a cation element in lithium silicate, namely an element L i, L i in the reducing agent L i and an oxide L i of the reducing agent2L i element in O, further to illustrate, when oxides CaO and MgO of the reducing agent and reducing agents Ca and Mg are also included in the composite, the elements Si, O, Ca and Mg in the composite are uniformly distributed.
Preferably, the mass percentage content of the reducing agent and/or the oxide of the reducing agent is 0.5 to 50%, for example, 0.5%, 1%, 1.5%, 2%, 3%, 3.5%, 4%, 5%, 8%, 10%, 13%, 16%, 20%, 25%, 28%, 30%, 35%, 40%, 42.5%, 45%, 50%, or the like, based on 100% of the total mass of the composite.
In a second aspect, the present invention provides a method of preparing a complex according to the first aspect, the method comprising the steps of:
(1) placing silicon oxide and/or a raw material for preparing silicon oxide and a reducing agent and/or a raw material for preparing the reducing agent in a vacuum furnace;
(2) heating and preserving heat under the negative pressure environment to obtain SiO steam and reducing agent steam, then condensing and discharging to obtain the compound.
In the present invention, the chemical composition of the silicon oxide is SiOxWherein 0 is<X<2。
The raw materials for preparing silicon oxide of the invention refer to: the reaction raw material required for preparing silicon oxide, preferably SiO2The reducing substance is preferably any one or a mixture of at least two of Si, C, Mg, Al, L i, Na, Ca, Zn, Fe or ferrosilicon powder, but is not limited to the above-listed reducing substances, and other reducing substances commonly used in the art may be used in the present invention.
For example, the raw materials for preparing silicon oxide can be: a mixture of silicon and silicon dioxide is used as a reaction raw material for preparing silicon oxide.
The invention discloses a silicon oxide and/or raw materials for preparing the silicon oxide, which refers to the following steps: the silicon oxide may be a raw material for preparing the silicon oxide, or a mixture of the silicon oxide and the raw material for preparing the silicon oxide.
The raw material for preparing the reducing agent in the invention refers to a reaction raw material required for preparing the reducing agent, and is preferably a mixture of an oxide of the reducing agent and/or a salt of the reducing agent and a reducing substance, wherein the oxide of the reducing agent can be L i for example2O、MgO、Al2O3、SiO2CaO, ZnO and Fe2O3The salt of the reducing agent may be, for example, L i2CO3、MgCO3、MgCl2、CaCO3And ZnCl2And the like, but not limited to the oxides of the reducing agents and the salts of the reducing agents listed above, and other salt minerals containing the reducing agent element may be used in the present invention, such as dolomite, quicklime, and the like.
Preferably, the reducing substance is any one or a mixture of at least two of Si, C, Mg, Al, L i, Na, Ca, Zn, Fe, or ferrosilicon powder, but is not limited to the above-listed reducing substances, and other reducing substances commonly used in the art may be used in the present invention.
By way of example, the starting materials for the preparation of the Mg reducing agent may be: the mixture of dolomite and ferrosilicon powder is used as a reaction raw material for preparing a reducing agent Mg. Another example may be: the mixture of quicklime and ferrosilicon powder is used as a reaction raw material for preparing the reducing agent Ca.
The "reducing agent and/or raw materials for preparing the reducing agent" in the invention refers to: the reducing agent may be used, or a raw material for producing the reducing agent may be used, or a mixture of the reducing agent and the raw material for producing the reducing agent may be used.
Wherein, when the raw materials for preparing silicon oxide are put into the vacuum furnace in the step (1), SiO steam is generated by the reaction raw materials in the temperature range of the invention; when the silicon oxide charged into the vacuum furnace in the step (1) is silicon oxide, the silicon oxide evaporates SiO vapor within the temperature range of the present invention.
When the raw materials which are put into the vacuum furnace in the step (1) are used for preparing the reducing agent, the reaction raw materials generate reducing agent steam within the temperature range of the invention; when the reducing agent is put into the vacuum furnace in the step (1), the reducing agent evaporates to form reducing agent vapor within the temperature range of the invention.
In the invention, in the process of heating and heat preservation in the negative pressure environment in the step (2), no matter SiO steam evaporated from silicon oxide or SiO steam generated from reaction raw materials, the SiO steam and reducing agent steam (reducing agent steam evaporated from a reducing agent at the reaction temperature of the invention and/or reducing agent steam generated from reaction raw materials at the temperature of the invention) are mixed with each other in a gaseous state, react, and are deposited and condensed into a solid material in a collecting chamber, so that the uniformity of the product is particularly good, and Si, O and reducing agent elements in the obtained product are uniformly distributed.
Preferably, the reducing agent in step (1) is any one or a mixture of at least two of L i, Na, Mg, Al, Ca, Zn and Fe.
Preferably, the specific process of step (1) is any one of scheme a, scheme B or scheme C, wherein scheme a is: firstly, mixing silicon oxide and/or a raw material for preparing silicon oxide and a raw material for preparing a reducing agent and/or a raw material for preparing the reducing agent, and then putting the mixture into a vacuum furnace;
the scheme B comprises the following steps: placing silicon oxide and/or raw materials for preparing silicon oxide at one end of a vacuum furnace close to a furnace tail, and placing reducing agent and/or raw materials for preparing reducing agent at one end of the vacuum furnace close to a furnace mouth;
the scheme C comprises the following steps: the silicon oxide and/or the raw material for preparing the silicon oxide are/is placed at one end of the vacuum furnace close to a furnace mouth, and the reducing agent and/or the raw material for preparing the reducing agent are/is placed at one end of the vacuum furnace close to a furnace tail.
Preferably, the vacuum degree of the negative pressure environment in the step (2) is 0 to 5000Pa, for example, 0Pa, 50Pa, 100Pa, 200Pa, 300Pa, 450Pa, 600Pa, 800Pa, 1000Pa, 1250Pa, 1500Pa, 1700Pa, 2000Pa, 2300Pa, 2500Pa, 3000Pa, 3200Pa, 3600Pa, 4000Pa, 4500Pa, or 5000 Pa.
Preferably, the heating temperature in step (2) is 500 to 1500 ℃, such as 500 ℃, 600 ℃, 700 ℃, 800 ℃, 850 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1350 ℃, 1400 ℃ or 1500 ℃, preferably 1000 to 1400 ℃.
Preferably, the heat preservation time in the step (2) is 1-30 h, for example, 1h, 3h, 5h, 6h, 8h, 10h, 13h, 15h, 18h, 20h, 24h, 26h, 28h or 30h, and the like, and preferably 12-24 h.
Preferably, the temperature of the coagulation in the step (2) is 500 to 1000 ℃, for example, 500 ℃, 550 ℃, 600, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, or 1000 ℃.
Preferably, the temperature of the discharge in step (2) is not higher than 1000 ℃, such as 1000 ℃, 900 ℃, 800 ℃, 700 ℃, 600 ℃, 500 ℃, 400 ℃, 300 ℃, 200 ℃, 100 ℃, 50 ℃ or 30 ℃, etc.
In a third aspect, the present invention provides an anode material, the raw material components of which comprise the composite of the first aspect.
In a fourth aspect, the present invention provides a method for preparing the anode material according to the third aspect, the method comprising the steps of:
the composite of the first aspect is used as a raw material component, and the composite is fired to obtain a negative electrode material.
Preferably, the firing temperature is 500 to 1100 ℃, and may be, for example, 500 ℃, 600 ℃, 650 ℃, 700 ℃, 800 ℃, 850 ℃, 900 ℃, 1000 ℃, 1100 ℃, or the like.
Preferably, the sintering time is 2-20 h, for example, 2h, 3h, 4h, 5h, 6h, 8h, 10h, 12h, 15h, 16h, 18h or 20 h.
Preferably, the method for preparing the negative electrode material further comprises a step of optionally performing heat treatment on the composite before firing, wherein the heat treatment temperature is preferably 200-1000 ℃, such as 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 1000 ℃.
Preferably, the time of the heat treatment is preferably 0.5 to 16 hours, for example, 0.5 hour, 1 hour, 2 hours, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 13 hours, 15 hours or 16 hours.
In the invention, the heat treatment is carried out under the protection of inert gas, and the inert gas is any one or a mixture of at least two of nitrogen, argon, helium, neon, krypton and xenon.
As a preferable embodiment of the method for producing the anode material of the present invention, the method further includes a step of coating before firing.
Preferably, when the method comprises a heat treatment step, the step of coating is performed after the heat treatment and before firing.
Preferably, the coating is performed by any one of a gas phase coating method, a liquid phase coating method and a solid phase coating method.
As a further preferable technical solution of the method for preparing the anode material of the present invention, the method further includes any one or a combination of at least two of the steps of crushing, pickling, or classifying.
Preferably, the step of pulverizing adopts a method of any one of ball milling, jet milling, crushing and spheroidizing or a combination of at least two of the above methods.
Preferably, the acid used in the step of acid washing is any one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, chromic acid, or hydrofluoric acid, or a mixed acid of at least two thereof. But not limited to the acids listed above, other acids that react with the reducing agent and/or the oxide of the reducing agent in the present invention may also be used in the present invention.
Preferably, in the step of acid washing, the acid washing time is 0.2-12 h, for example, 0.2h, 0.5h, 0.8h, 1h, 2h, 3h, 4h, 5h, 6h, 8h, 9h, 10h, 11h or 12h, etc.
The acid in the present invention may be a concentrated acid or a dilute acid, but it is necessary to ensure that it can react with the reducing agent and/or the oxide of the reducing agent in the present invention.
In the present invention, the oxide of the reducing agent (e.g., L i) produced may be subjected to an acid washing step2O、Na2O、MgO、Al2O3CaO, ZnO and Fe2O3Etc.), oxides of reducing substances (e.g. SiO2MgO and Al2O3Etc.), residual reducing agent (e.g., L i, Na, Mg, Al, Ca, Zn, Fe, etc.) or residual reducing species (e.g., Mg, Al, etc.).
Preferably, in the step of classifying, the classified average particle diameter D50 is 1 to 100 μm, and the specific surface area is 1 to 120m2Material/g. D50 is, for example, 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 80 μm or 100 μm. A specific surface area of, for example, 1m2/g、10m2/g、20m2/g、30m2/g、40m2/g、50m2/g、60m2/g、80m2/g、100m2/g、110m2G or 120m2And/g, etc.
Preferably, when the method includes the steps of heat treatment, pulverization and classification at the same time, it is carried out according to any one of scheme I, scheme II or scheme III,
wherein, the scheme I is as follows: crushing, grading and finally heat treatment.
The scheme II comprises the following steps: crushing, heat treatment and grading.
The scheme III is as follows: heat treatment, crushing and grading.
In a fifth aspect, the present invention provides a lithium ion battery comprising the negative electrode material of the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the elements in the compound are good in dispersion uniformity, and an energy spectrometer (EDS) is adopted to detect the compound, so that the results show that the Si, O and reducing agent elements in the compound are uniform in distribution and high in consistency.
(2) Compared with the traditional SiO electrode material, the modified silica anode material prepared by adopting the compound as the raw material component reduces a part of SiO by using a reducing agent, so that the O content in the material is reduced, and the obtained modified silica anode material can obviously reduce the irreversible phase L i generated by the reaction of SiO and L i particles in the anode material during the first charging when being applied to an electrode2The amount of O finally reduces the irreversible capacity of the material, improves the coulombic efficiency of the material, has the first coulombic efficiency of more than 83.8 percent, and solves the problem of low first coulombic efficiency of the SiO negative electrode material; moreover, the consumption of the lithium which is irreversibly charged at the positive electrode can be reduced, the energy density of the full battery is improved, the separation of irreversible lithium at the negative electrode is avoided, and potential safety hazards are eliminated.
(3) The preparation methods of the composite and the cathode material are simple and feasible, the raw materials are low in price, and the industrial implementation is easy.
Drawings
FIG. 1 shows a modified SiO film obtained in example 1XAn X-ray diffraction pattern of the material;
FIG. 2 shows a modified SiO solid obtained in example 1XScanning electron microscope images of the cathode material;
FIG. 3 shows a modified SiO solid obtained in example 1XA sectional view of the anode material;
FIG. 4a shows a modified SiO solid obtained in example 1XA sectional view of the anode material;
FIG. 4b is a schematic diagram of the element distribution result obtained by scanning the cathode material in FIG. 4a from left to right along the marked lines;
FIG. 5 is a view showing SiO obtained in comparative example 1XAn X-ray diffraction pattern of the material;
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Carrying out charge and discharge tests on the prepared simulated battery, wherein the test steps and conditions are 1 and 2 hours of rest; 2. discharging at 0.1 deg.C to voltage not more than 0.01V; 3. discharging at 0.02C to voltage less than or equal to 0.005V; 4. standing for 3 h; 5. charging to 0.1C until the voltage is more than or equal to 1.5V; 6. standing for 3 h; 7. the charge and discharge cycles were carried out and the test results are shown in table 1.
Example 1
Synthesis of the complex:
(1) taking 5Kg of Si powder and 10Kg of SiO2Putting the powder into a VC mixer to be mixed for 30min to obtain SiO2And Si, and putting the mixture into one end of the vacuum furnace close to the tail of the furnace as a raw material for preparing silicon oxide;
(2) taking 10Kg of dolomite and 5Kg of ferrosilicon powder, putting into a VC mixer, mixing for 30min to obtain a mixture of 15Kg of dolomite and ferrosilicon powder, and putting the mixture serving as a raw material for preparing Mg into one end of a vacuum furnace close to a furnace mouth;
(3) placing a collector in the collecting chamber, heating to 1350 deg.C under vacuum degree of 3Pa, maintaining for 24 hr to generate SiO steam and Mg steam, rapidly condensing the uniformly mixed gaseous mixture (condensation temperature is 900 deg.C) to obtain SiOx-Mg material named as modified SiOXThe material, after the reaction is finished, the equipment is cooled and 15Kg of product is collected.
The SiOx-Mg material obtained by the invention contains silicon and silicon oxide SiOxX is more than 0 and less than or equal to 2, and magnesium silicate does not contain Mg simple substance.
Testing of the complexes:
modified SiO prepared in this example was subjected to X-ray diffractometryXThe material is qualitatively analyzed, and the detection result is obtainedAs shown in FIG. 1, it can be seen that the modified SiO preparedXThe material has a characteristic peak of magnesium silicate generated after the reaction of Mg and SiO and a characteristic peak of Si, and has no peak of Mg simple substance, which indicates that the magnesiothermic reduction reaction is carried out completely, and SiO is silicon oxidex(0 < x < 2) is amorphous and thus not shown in the XRD pattern.
Synthesis of modified silicon-oxygen negative electrode material:
(A) and (3) heat treatment: taking 10Kg of modified SiOXThe material is put into a roller kiln with nitrogen as protective gas for heat treatment at 600 ℃, and the granularity of the material after heat treatment is controlled to be about 4 mu m by the processes of crushing, ball milling, grading and the like.
(B) Acid washing: mixing the above modified SiO of 4 μmXAdding the material into a 20 wt% hydrochloric acid solution, carrying out acid washing for 4h, then washing the material to be neutral by using deionized water, and drying.
(C) Coating: drying the modified SiOXThe material is placed in a CVD furnace, nitrogen is introduced into the outer path as protective gas, methane gas is introduced into the inner path as carbon source, the temperature is increased to 900 ℃ to decompose methane, the nitrogen flow is set to be 3.5L/min during reaction, and 5 wt% of carbon is coated on the surface of the cathode material.
(D) And (3) firing: after the coating is finished, the obtained material is placed in a roller kiln for high-temperature carbonization at 960 ℃ to obtain stable modified SiOXAnd (3) a negative electrode material.
Testing of the modified silicon-oxygen anode material:
the modified SiO prepared in this example was observed by scanning electron microscopeXThe morphology structure of the cathode material is shown in FIG. 2, and the modified SiO can be seenXThe surface of the negative electrode material is fully coated with C decomposed by methane.
The modified SiO prepared in this example was subjected to an energy spectrometer and a scanning electron microscopeXThe negative electrode material was tested, and FIG. 3 shows modified SiOXScanning electron microscope image of the cathode material, FIG. 4 is modified SiOXThe element distribution diagram of the section of the anode material shows that the C element and the Mg element are uniformly distributed in the material.
A simulated battery is made of the negative electrode material, the charge and discharge performance of the simulated battery is tested, the first charge capacity of the simulated battery is 1587mAh/g, the first discharge capacity of the simulated battery is 1338mAh/g, and the first efficiency of the simulated battery is 84.3%.
Example 2
Except that during the synthesis of the complex, the operations of step (1) and step (2) were changed to: the obtained SiO2The mixture with Si and the resulting raw material for Mg production were mixed, and the mixed mixture was charged into a vacuum furnace, and the other production methods and conditions were the same as in example 1.
Testing of the complexes:
the compound prepared in this example was qualitatively analyzed by an X-ray diffractometer, and the detection result was similar to that shown in fig. 1 of example 1, and the compound prepared exhibited a characteristic peak of magnesium silicate generated after the reaction of Mg and SiO and a characteristic peak of Si, and did not exhibit a peak of Mg simple substance. Silicon oxide SiOx(0<x.ltoreq.2) is amorphous and is therefore not shown in the XRD pattern.
In the compound obtained by the invention, SiO comprises silicon and silicon oxidex，0<x is less than or equal to 2, and magnesium silicate does not contain Mg simple substance.
Testing of the modified silicon-oxygen anode material:
the morphology structure of the modified silica anode material prepared in the embodiment is observed by using a scanning electron microscope, and the result shows that the surface of the modified silica anode material is fully wrapped with C decomposed by methane.
The modified silica anode material prepared in the embodiment is tested by using an energy spectrometer and a scanning electron microscope, and the result shows that the C element and the Mg element are uniformly distributed in the material.
A simulated battery is prepared from the modified silica negative electrode material, the charge-discharge performance of the simulated battery is tested, the first charge capacity of the simulated battery is 1653mAh/g, the first discharge capacity of the simulated battery is 1389mAh/g, and the first efficiency of the simulated battery is 84.0%.
Example 3
Except that in the synthesis process of the complex, the operations of the step (1) and the step (2) are replaced by: the raw material for Mg preparation was replaced by 2Kg of magnesium powder and this was mixed with the SiO obtained2Mixing with Si, and placing in a vacuum furnaceThe preparation method and conditions were the same as in example 1.
Testing of the complexes:
the compound prepared in this example was qualitatively analyzed by an X-ray diffractometer, and the detection result was similar to that shown in fig. 1 of example 1, and the prepared compound exhibited a characteristic peak of silicate generated after the reaction of Mg and SiO and a characteristic peak of Si, and did not exhibit a peak of Mg simple substance.
Silicon oxide SiOx(0<x.ltoreq.2) is amorphous and is therefore not shown in the XRD pattern.
In the compound obtained by the invention, SiO comprises silicon and silicon oxidex，0<x is less than or equal to 2, and magnesium silicate does not contain Mg simple substance.
Testing of the modified silicon-oxygen anode material:
the morphology structure of the modified silica negative electrode material prepared in the embodiment is observed by using a scanning electron microscope, and the result shows that the surface of the negative electrode material is fully coated with C decomposed by methane.
The modified silica anode material prepared in the embodiment is tested by using an energy spectrometer and a scanning electron microscope, and the result shows that the C element and the Mg element are uniformly distributed in the material.
A simulated battery is prepared from the modified silica negative electrode material, the charge-discharge performance of the simulated battery is tested, the first charge capacity of the simulated battery is 1492mAh/g, the first discharge capacity of the simulated battery is 1261mAh/g, and the first efficiency of the simulated battery is 84.5%.
Example 4
The preparation method and conditions were the same as in example 1 except that the acid washing in step (B) was not performed during the synthesis of the anode material.
The results of the complex testing are exactly the same as in example 1, see example 1.
Testing of the modified silicon-oxygen anode material:
the morphology structure of the modified silica anode material prepared in the embodiment is observed by using a scanning electron microscope, and the result shows that the surface of the modified silica anode material is fully wrapped with C decomposed by methane.
The modified silica anode material prepared in the embodiment is tested by using an energy spectrometer and a scanning electron microscope, and the result shows that the element C and a small amount of the element Mg are uniformly distributed in the material.
A simulated battery is prepared from the modified silica negative electrode material, the charge-discharge performance of the simulated battery is tested, the first charge capacity of the simulated battery is 1213mAh/g, the first discharge capacity of the simulated battery is 1447mAh/g, and the first efficiency of the simulated battery is 83.8%.
Example 5
Synthesis of the complex:
(1) taking 5Kg of Si powder and 10Kg of SiO2Putting the powder into a VC mixer to be mixed for 30min to obtain SiO2And Si; putting the mixture serving as a raw material for preparing silicon oxide into one end of a vacuum furnace close to the tail of the furnace;
taking 10Kg of quicklime and 5Kg of ferrosilicon powder, putting into a VC mixer, mixing for 30min to obtain a mixture of 15Kg of quicklime and ferrosilicon powder, and putting the mixture serving as a raw material for preparing Ca into one end of a vacuum furnace close to a furnace mouth;
(2) and (3) placing a collector in a collecting chamber, heating to 1300 ℃ under the negative pressure condition of 5Pa of vacuum degree, preserving heat for 24h to generate SiO steam and Ca steam in the furnace, and quickly condensing the uniformly mixed gaseous mixture (the condensing temperature is 950 ℃) to generate the SiOx-Ca material.
The SiOx-Ca material obtained by the invention contains silicon and silicon oxide SiOx，0<x is less than or equal to 2, calcium silicate does not contain calcium simple substance.
Testing of the complexes:
the SiOx-Ca material prepared in this example was qualitatively analyzed by an X-ray diffractometer, and the detection result was similar to that of example 1, and the prepared SiOx-Ca material had a characteristic peak of calcium silicate and a characteristic peak of Si generated after the reaction between Ca and SiO, and had no peak of calcium simple substance, which indicates that the reduction reaction proceeded more thoroughly, and the silicon oxide SiO was more completely reducedx(0<x.ltoreq.2) is amorphous and is therefore not shown in the XRD pattern.
Synthesis of modified silicon-oxygen negative electrode material:
(A) and (3) heat treatment: the prepared SiOx-Ca material is put into a roller kiln with nitrogen as protective gas for heat treatment at 400 ℃, and the granularity of the material after heat treatment is controlled to be about 10 mu m D50 through the processes of crushing, ball milling, grading and the like.
(B) Acid washing: and adding the 10-micron SiOx-Ca material into a 15 wt% hydrochloric acid solution, carrying out acid washing for 4h, washing the material to be neutral by using deionized water, and drying.
(C) And (3) coating, namely placing the dried SiOx-Ca material in a CVD furnace, introducing helium as a protective gas into an outer path, introducing methane gas as a carbon source into an inner path, heating to 900 ℃ to decompose methane, setting the nitrogen flow at 3.5L/min during reaction, and coating 5 wt% of carbon on the surface of the cathode material.
(D) And (3) firing: after the coating is finished, the obtained material is placed in a roller kiln for high-temperature carbonization at 960 ℃ to obtain the stable modified silica negative electrode material.
Testing of the modified silicon-oxygen anode material:
the morphology structure of the modified silica anode material prepared in the embodiment is observed by using a scanning electron microscope, and the result shows that the surface of the modified silica anode material is fully wrapped with C decomposed by methane.
The anode material prepared in the present example was tested using an energy spectrometer and a scanning electron microscope, and the results showed that the C element and Ca element were uniformly distributed in the material.
The modified silica negative electrode material is used for preparing a simulation battery and testing the charge and discharge performance of the simulation battery, and the first charge capacity is 1310mAh/g, the first discharge capacity is 1576mAh/g and the first efficiency is 83.1 percent.
Example 6
(1) Putting 10Kg of SiO powder into one end of the vacuum furnace close to the furnace tail;
5Kg of Mg powder is put into one end of the vacuum furnace close to the furnace mouth;
(2) and (3) placing a collector in a collecting chamber, heating to 1250 ℃ under the negative pressure condition of the vacuum degree of 3Pa, preserving heat for 30h to generate SiO steam and Mg steam in the furnace, and quickly condensing the uniformly mixed gaseous mixture (the condensing temperature is 900 ℃) to generate the SiOx-Mg material.
The SiOx-Mg material obtained by the invention contains silicon and silicon oxide SiOxX is more than 0 and less than or equal to 2, and magnesium silicate does not contain magnesium simple substance.
Testing of the complexes:
qualitative analysis was performed on the SiOx-Mg material prepared in this example by using an X-ray diffractometer, and the detection result was similar to that in example 1, a characteristic peak of magnesium silicate and a characteristic peak of Si generated after the reaction between Mg and SiO were present in the prepared SiOx-Mg material, and a peak of a simple substance of Mg was not present, which indicates that the magnesiothermic reduction reaction was performed more thoroughly, and the silicon oxide SiO was presentx(0<x.ltoreq.2) is amorphous and is therefore not shown in the XRD pattern.
Synthesis of modified silicon-oxygen negative electrode material:
(A) and (3) heat treatment: the SiOx-Mg material is taken and put into a roller kiln with argon as protective gas for heat treatment at 700 ℃, and the granularity of the material after heat treatment is controlled to be about 5 mu m by the processes of crushing, ball milling, grading and the like.
(B) Acid washing: and adding the 5-micron SiOx-Mg material into a 15 wt% hydrochloric acid solution, carrying out acid washing for 6h, then washing the material to be neutral by using deionized water, and drying.
(C) And (3) coating, namely placing the dried SiOx-Mg material in a CVD furnace, introducing nitrogen as a protective gas into the outer path, introducing methane gas as a carbon source into the inner path, heating to 950 ℃ to decompose methane, setting the nitrogen flow at 3.5L/min during reaction, and coating 5 wt% of carbon on the surface of the cathode material.
(D) And (3) firing: and after the coating is finished, putting the obtained material in a roller kiln for high-temperature carbonization at 1000 ℃ to obtain the stable modified silica negative electrode material.
Testing of the modified silicon-oxygen anode material:
the morphology structure of the modified silica anode material prepared in the embodiment is observed by using a scanning electron microscope, and the result shows that the surface of the modified silica anode material is fully wrapped with C decomposed by methane.
The modified silica anode material prepared in the embodiment is tested by using an energy spectrometer and a scanning electron microscope, and the result shows that the C element and the Mg element are uniformly distributed in the material.
A simulated battery is prepared from the modified silica negative electrode material, the charge and discharge performance of the simulated battery is tested, the first charge capacity of the simulated battery is 1612mAh/g, the first discharge capacity of the simulated battery is 1346mAh/g, and the first efficiency of the simulated battery is 83.5%.
Comparative example 1
Except that in the synthesis of the complex, step (1) is followed by step (3) without step (2); and in the synthesis process of the anode material, after the step (A), the step (C) is directly carried out without carrying out the step (B) acid washing, and other preparation methods and conditions are the same as those of the example 1.
The obtained negative electrode material was tested:
the negative electrode material obtained in the present comparative example was qualitatively analyzed by an X-ray diffractometer, and the detection result is shown in fig. 5, from which it is seen that the obtained material has only a characteristic peak of Si.
Testing the negative electrode material obtained in the step (D):
observing the morphology structure of the negative electrode material obtained in the step (D) of the comparative example on a scanning electron microscope, and observing that the surface of the negative electrode material is coated with C after methane decomposition.
The anode material is used for manufacturing a simulation battery and testing the charge and discharge performance of the simulation battery, and the first charge capacity is 2040mAh/g, the first discharge capacity is 1563mAh/g and the first efficiency is 76.6 percent.
Table 1 is a table comparing the charge and discharge test results and the initial cycle battery performance of examples 1 to 6 and comparative example 1.
TABLE 1
From the comparative data, the electrochemical properties such as the first coulombic efficiency and the like of the modified silica negative electrode material prepared by the method are superior to those of the negative electrode material in the comparative example.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (27)
1. A compound comprising silicon, silicon oxide and a silicate, wherein a cation element in the silicate is a reducing agent element, and Si, O and the reducing agent element are uniformly distributed;
wherein the chemical composition of the silicon oxide is SiOx，0<x≤2；
The compound is prepared by adopting the following method, and the preparation method comprises the following steps:
(1) placing raw materials for preparing silicon oxide and a reducing agent and/or raw materials for preparing the reducing agent in a vacuum furnace;
(2) heating and preserving heat in a negative pressure environment to obtain SiO steam and reducing agent steam, condensing, and discharging to obtain a compound;
the heating temperature in the step (2) is 1000-1400 ℃, the heat preservation time in the step (2) is 12-24 hours, the condensation temperature in the step (2) is 500-1000 ℃, and the vacuum degree in the negative pressure environment in the step (2) is 0-5000 Pa.
2. The composite of claim 1, wherein the composite further comprises a reducing agent and/or an oxide of the reducing agent, and the Si, O and the reducing agent element in the composite are uniformly distributed, and the reducing agent element is derived from the silicate and the reducing agent and/or the oxide of the reducing agent.
3. The composite according to claim 1, wherein the reducing agent is any one or a mixture of at least two of L i, Na, Mg, Al, Ca, Zn, or Fe.
4. The composite according to claim 1, wherein the mass percentage of the reducing agent and/or the oxide of the reducing agent is 0.5 to 50% based on 100% of the total mass of the composite.
5. A method of preparing a composite according to claim 1, comprising the steps of:
(1) placing raw materials for preparing silicon oxide and a reducing agent and/or raw materials for preparing the reducing agent in a vacuum furnace;
(2) heating and preserving heat in a negative pressure environment to obtain SiO steam and reducing agent steam, condensing, and discharging to obtain a compound;
the heating temperature in the step (2) is 1000-1400 ℃, the heat preservation time in the step (2) is 12-24 hours, the condensation temperature in the step (2) is 500-1000 ℃, and the vacuum degree in the negative pressure environment in the step (2) is 0-5000 Pa.
6. The method for preparing a composite according to claim 5, wherein the raw material for preparing the silicon oxide is SiO2And a reducing substance.
7. The method for producing a composite according to claim 5, wherein the raw material for producing the reducing agent is a mixture of an oxide of the reducing agent and/or a salt of the reducing agent and a reducing substance.
8. The method for producing a composite according to claim 6 or 7, wherein the reducing substance is any one of or a mixture of at least two of Si, C, Mg, Al, L i, Na, Ca, Zn, Fe, or ferrosilicon powder.
9. The method for preparing a composite according to claim 5, wherein the reducing agent in step (1) is any one or a mixture of at least two of L i, Na, Mg, Al, Ca, Zn and Fe.
10. The method for preparing a complex according to claim 5, wherein the specific process of step (1) is any one of scheme A, scheme B or scheme C,
wherein the scheme A comprises the following steps: mixing the raw materials for preparing silicon oxide and the reducing agent and/or the raw materials for preparing the reducing agent, and then putting the mixture into a vacuum furnace;
the scheme B comprises the following steps: placing the raw material for preparing silicon oxide in one end of a vacuum furnace close to the tail of the furnace, and placing the reducing agent and/or the raw material for preparing the reducing agent in one end of the vacuum furnace close to the mouth of the furnace;
the scheme C comprises the following steps: the raw material for preparing silicon oxide is placed at one end of the vacuum furnace close to a furnace mouth, and the reducing agent and/or the raw material for preparing the reducing agent are placed at one end of the vacuum furnace close to a furnace tail.
11. The method of claim 5, wherein the temperature of the output of step (2) is not greater than 1000 ℃.
12. A negative electrode material, characterized in that a raw material component of the negative electrode material comprises the composite according to any one of claims 1 to 4.
13. The method for preparing the anode material according to claim 12, comprising the steps of:
the composite according to claim 1 or 2 as a raw material component, and firing the composite to obtain a negative electrode material.
14. The method for producing the anode material according to claim 13, wherein the firing temperature is 500 to 1100 ℃.
15. The method for producing the anode material according to claim 13, wherein the firing time is 2 to 20 hours.
16. The method for preparing the negative electrode material according to claim 13, further comprising a step of optionally heat-treating the composite before firing, wherein the heat treatment temperature is 200 to 1000 ℃.
17. The preparation method of the anode material according to claim 16, wherein the heat treatment time is 0.5-16 h.
18. The method for preparing the negative electrode material according to claim 16, wherein the heat treatment is performed under protection of an inert gas, and the inert gas is any one of nitrogen, argon, helium, neon, krypton, and xenon, or a mixture of at least two of the nitrogen, argon, helium, neon, krypton, and xenon.
19. The method for producing the anode material according to claim 13, further comprising a step of coating before firing.
20. The method for producing the anode material according to claim 19, wherein when a heat treatment step is included in the method, the step of coating is performed after the heat treatment and before firing.
21. The method for manufacturing the anode material according to claim 19, wherein the coating is performed by any one of a vapor phase coating method, a liquid phase coating method, and a solid phase coating method.
22. The method for producing the anode material according to claim 13, further comprising any one of or a combination of at least two of the steps of pulverization, acid washing, or classification.
23. The method for preparing the anode material according to claim 22, wherein the step of pulverizing is performed by any one of ball milling, crushing, or spheroidizing or a combination of at least two of them.
24. The method for producing the anode material according to claim 22, wherein in the step of acid-washing, an acid used is any one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, chromic acid, and hydrofluoric acid, or a mixed acid of at least two of them.
25. The method for preparing the anode material according to claim 22, wherein in the step of acid washing, the acid washing time is 0.2-12 hours.
26. The method for producing the anode material according to claim 22, wherein in the classifying step, the classified average particle diameter D50 is 1 to 100 μm, and the specific surface area is 1 to 120m2Material/g.
27. The method according to claim 13, wherein when the method comprises the steps of heat treatment, pulverization and classification, the method is carried out according to any one of scheme I, scheme II or scheme III,
wherein, the scheme I is as follows: crushing, grading and finally performing heat treatment;
the scheme II comprises the following steps: crushing, heat treatment and grading at last;
the scheme III is as follows: heat treatment, crushing and grading.
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