CN116093300A - Simple pre-lithium metal doped silicon oxygen carbon negative electrode material and preparation method thereof - Google Patents

Simple pre-lithium metal doped silicon oxygen carbon negative electrode material and preparation method thereof Download PDF

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CN116093300A
CN116093300A CN202211556745.7A CN202211556745A CN116093300A CN 116093300 A CN116093300 A CN 116093300A CN 202211556745 A CN202211556745 A CN 202211556745A CN 116093300 A CN116093300 A CN 116093300A
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silicon oxide
lithium
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doped silicon
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霍锋
刘凡
刘艳侠
柴丰涛
刘景博
杨宝玉
高哲
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Zhengzhou Institute of Emerging Industrial Technology
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Abstract

The invention relates to a simple pre-lithium metal doped silicon-oxygen-carbon anode material and a preparation method thereof, and the material is prepared through two different spray drying and one sintering processes. Forming a carbon film with a uniformly coated surface by primary spray drying, and introducing metal active substances; protecting and introducing active lithium source in the secondary spray drying process, and reacting active lithium source with silicon oxygen to generate Li in the sintering process 2 SiO 3 Layer, li 2 SiO 3 Formed by a layer and sintering processThe first modified carbon layer and the second modified carbon layer together form a multi-stage coating of the silica surface. Li (Li) 2 SiO 3 The generation of irreversible substances in the charge and discharge process can be inhibited, and the first effect is improved; the multistage cladding structure can effectively buffer the volume expansion in the process of charging and discharging the silicon oxide, and improve the stability; the metal doping improves the structural stability, improves the electrochemical activity of the material and forms a compact interface. The material has the advantages of strong water resistance, stable structure, high capacity, high coulomb efficiency, stable circulation and good application prospect.

Description

Simple pre-lithium metal doped silicon oxygen carbon negative electrode material and preparation method thereof
Technical Field
The invention relates to the field of electrochemistry, in particular to a simple pre-lithium metal doped silicon-oxygen-carbon anode material and a preparation method thereof.
Background
The growing exhaustion of non-renewable energy sources is increasingly in conflict with the demand for energy by social development. Lithium batteries have been widely used in various fields of production and life as a representative of secondary batteries. In face of the urgent need of energy storage density improvement, the low theoretical capacity (about 372 mAh/g) of the traditional graphite negative electrode material can not meet the requirement of a high-energy-density battery. Si has better theoretical capacity>3500 mAh/g) is considered to be the most promising new material to replace graphite anodes, however the higher volume expansion limits its commercialization progress. Silicon oxide (SiO) x ) Is a derivative material of Si, also has higher theoretical specific capacity, and is formed by Li generated by the first lithium intercalation process 2 O、Li 2 SiO 4 The first effect of the inert substances is lower, but the generation of the inert substances is distributed in the material to better relieve the volume change of the material, so that the material has the advantage of stable circulation. Comparison with Si, siO x Has more excellent industrial application prospect.
SiO x In the commercialization process, the problems of low initial coulomb efficiency, large expansion and poor conductivity still need to be solved, and the uniform and stable coating of the surface is the most critical improvement strategy, and for macro preparation, the coating is carried outUniformity is the most difficult to achieve and is one of the key indicators. The existence of oxygen element in silica forms lithium silicate, lithium oxide and other irreversible lithium removal substances inside the particles, so that irreversible loss of lithium ions inside the battery is caused. Silicon oxide also has the problem of low ionic and electronic conductivity and is a key factor affecting the performance of materials. Based on the above problems, researchers have made various improvements including strategies of surface uniform carbon coating, addition of a material excellent in conductivity, and preliminary consumption of internal oxygen elements, as follows.
CN 112331838A discloses a high-capacity silicon oxide composite negative electrode material of a lithium ion battery and a preparation method thereof, silicon oxide is added into a protonated chitosan solution, then spray drying and sintering are carried out to obtain a carbon-coated silicon oxide material, and then spray drying is carried out after mixing with conductive carbon and lithium salt according to a certain proportion to obtain the high-capacity silicon oxide composite material. However, the inert lithium source component added in the material has limited effect on improving the first efficiency of the silicon oxide, and the conductive carbon and the lithium source doped by spray drying after sintering are easy to fall off and lose efficacy in the subsequent slurry preparation process.
CN 115207312A discloses a double-shell silica material and a preparation method thereof, the silica material is added into an organic substance and carbon nanotube precursor solution, dried and sintered to obtain a first protective layer, and then mixed and sintered with the organic substance precursor to obtain a second coating layer. The method has poor controllability, the complete uniformity of the coating layer is difficult to control by drying after liquid phase mixing and solid phase mixing, the pre-lithium effect is difficult to achieve, and the first effect of the material is low, so that the industrialized application is restricted.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a simple pre-lithium metal doped silicon-oxygen-carbon negative electrode material and a preparation method thereof, wherein the material is mainly formed through two-step differential spray drying and one-step sintering processes, realizes multistage stable coating of a silicon-oxygen surface, inhibits volume expansion, improves overall conductivity, and relieves side reactions of the surface and electrolyte. Li formed by active lithium and silicon oxide surface sintering process 2 SiO 3 The layer can inhibit irreversible substances in charge and discharge processThe formation improves the first effect, and the metal doping can improve the structural stability, improve the electrochemical activity and form a compact interface, thereby improving the stability of the lithium silicon oxide. The silicon-carbon negative electrode obtained by the preparation method has the advantages of high initial effect, good stability and rate capability, is suitable for the negative electrode of the power battery, has simple process and industrialization prospect, and provides technical reference for technical improvement and product upgrading of the negative electrode material of the lithium ion battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
a simple pre-lithium metal doped silicon oxygen carbon negative electrode material comprises silicon oxide, wherein a first modified carbon layer is coated outside the silicon oxide, a second modified carbon layer is coated outside the first modified carbon layer, and a metal active substance and conductive carbon are contained in the first modified carbon layer; the second modified carbon layer contains an active pre-lithium agent and conductive carbon, and the active pre-lithium agent reacts with silicon oxide to form a layer of Li on the surface 2 SiO 3 And a layer, wherein the first modified carbon layer and the second modified carbon layer together form a multi-stage coating layer on the surface of the silicon oxide.
Further, the silica particle size is 3 to 5 μm, wherein the silica ratio=0.9 to 1.1; the mass content of the silicon oxide is 70-95%, the mass content of the first modified carbon layer is 0.1-10%, the mass content of the second modified carbon layer is 0.1-10%, the mass content of the total conductive carbon is 0.5-2%, the mass content of the metal active substance is 0.1-5%, and the molar ratio of the silicon oxide to the active pre-lithium agent is 20:1-6:1.
The simple pre-lithium metal doped silicon-oxygen-carbon negative electrode material is prepared through two different spray drying and one-time sintering processes, a first carbon coating layer is formed on the surface of silicon oxide through one-time spray drying, and meanwhile, a metal active substance is introduced; the second spray drying realizes the second uniform coating of the surface, and simultaneously introduces an active pre-lithium agent; the carbon source is coated twice in the sintering process to form a first modified carbon layer and a second modified carbon layer, and simultaneously the active pre-lithium agent reacts with the silicon oxide to form a layer of Li on the surface 2 SiO 3 A layer, which forms a multi-stage coating layer on the surface of the silicon oxide together with the first modified carbon layer and the second modified carbon layer; spray drying for the first time with water as solvent, selectingThe carbon source dissolved in water is used as a coating agent, and preferably can react with hydroxyl groups on the surface of the silicon oxide to form a compact carbon layer; the secondary spray drying solvent is an anhydrous organic solvent, and a carbon source dissolved in the organic solvent is selected, so that the anhydrous organic solvent plays a role in protecting an active lithium source; wherein the first modified carbon layer and the second modified carbon layer both contain a small amount of conductive carbon.
Further, the preparation method of the simple pre-lithium metal doped silicon-oxygen-carbon anode material comprises the following specific preparation processes:
(1) Preparing an acidic aqueous solution with the pH of 3, adding a carbon source A, carrying out ultrasonic treatment and uniformly stirring to obtain an aqueous solution B;
(2) Adding silicon oxide into the aqueous solution B, simultaneously dropwise adding the conductive carbon aqueous solution C, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid D;
(3) Adding metal salt M into the dispersion D, stirring uniformly to obtain a dispersion C, and spray-drying to obtain a silicon-oxygen-carbon precursor E;
(4) Adding a carbon source F into an anhydrous organic solvent, simultaneously dropwise adding a conductive carbon solution G, performing ultrasonic treatment and uniformly stirring to obtain a dispersion liquid H;
(5) Adding the silicon oxide precursor E into the dispersion liquid H, adding an active pre-lithium agent solution, uniformly stirring, and then performing spray drying to obtain a silicon oxide precursor I;
(6) And (3) placing the silicon oxide precursor I into a tube furnace for inert atmosphere protection high-temperature sintering, cooling, crushing and sieving with a 300-mesh sieve to obtain the pre-lithium metal doped silicon oxide carbon negative electrode material.
Further, the acid in the acidic aqueous solution in the step (1) is citric acid, acetic acid, hydrochloric acid, sulfuric acid or phytic acid; the carbon source A is one or more of chitosan, glucose, sucrose, polyvinyl alcohol, polyvinylpyrrolidone or sodium alginate.
Further, the conductive carbon in the step (2) and the step (4) is one of carbon nanotubes, graphene or conductive fibers, and the solid content is 0.1-2%, preferably 0.4-1%; wherein the conductive carbon solution G in the step (4) adopts one of ethanol, methanol, ethylene glycol, ethyl acetate and azomethine formamide.
Further, the metal salt M in the step (3) is Fe, co, ni, mg, ca or Zn chloride, nitrate, citrate or acetate; the anhydrous organic solvent in the step (4) is ethanol, methanol, glycol, isopropanol, ethyl acetate or azomethine formamide; the carbon source F in the step (4) is phenolic resin, acrylic resin, polyethylene glycol, polyvinylpyrrolidone, cellulose, polystyrene, citric acid or stearic acid.
Further, in the step (5), the active pre-lithium agent solution is a tetrahydrofuran solution of hexamethyldisilazide lithium, tri-sec-butylborohydride lithium or triethylborohydride lithium, and the concentration of the active pre-lithium agent solution is 1M.
Further, the spray drying inlet temperature in the step (3) is 140-200 ℃, the outlet temperature is 90-110 ℃, the feeding speed is 3-12 rad/min, the air atmosphere is adopted, and the spray pressure is 0.2MPa; the spray drying inlet temperature in the step (5) is 150-190 ℃, the outlet temperature is 90-110 ℃, the feeding speed is 5-12 rad/min, and the nitrogen atmosphere is adopted.
Further, the sintering condition in the step (6) is two-stage sintering: heating to 250 ℃ at normal temperature, wherein the heating rate is 5 ℃/min, and preserving heat for 2 hours; heating to 700-1000 deg.C at 3 deg.C/min, maintaining for 2-4 hr, naturally cooling, and using high purity argon with purity of 99.999% as shielding gas.
The beneficial effects of the invention are as follows: the material is prepared through two different spray drying and one sintering processes. (1) Forming a first coated carbon layer on the surface of the silicon oxide by primary spray drying, introducing metal doped active sites, and carrying out acid treatment on a protonated carbon source to realize firm combination of the carbon layer and the surface of the silicon oxide; (2) The secondary uniform coating is realized by the secondary spray drying, the organic solvent system ensures the stability of the active lithium source, and the formed carbon layer plays a role in protecting the lithium source, and the secondary carbon coating can strengthen the effect of the first carbon coating, thereby playing a role in further improving the stability; protecting and introducing active lithium source in the second spray drying process, and reacting active lithium source with silicon oxygen to generate Li in the sintering process 2 SiO 3 A layer incorporating an external second modificationA carbon layer; (3) The conductive carbon added into the twice spray-drying slurry can ensure the penetrating distribution of conductive components in the spraying and sintering processes, thereby realizing a conductive network from outside to inside; (4) The active lithium source reacts with silicon oxide in the sintering process to form a layer of Li on the surface 2 SiO 3 Layer, li 2 SiO 3 The layer together with the first and second modified carbon layers formed during sintering form a multi-stage coating of the silicon oxygen surface. (5) The sintering treatment is carried out after the secondary spray drying coating, so that the internal metal components, conductive carbon and Li can be ensured 2 SiO 3 All are in the carbon layer of the outer amorphous carbon, so that the falling of components in the process of preparing the pole piece by subsequent slurry mixing is avoided, and an integral and complete material structure is formed. Li (Li) 2 SiO 3 The formation of the polymer can inhibit the generation of irreversible substances in the charge and discharge process, and the first effect is improved; the multistage cladding structure can effectively buffer the volume expansion in the process of charging and discharging the silicon oxide, and improve the stability; the metal doping improves the structural stability, improves the electrochemical activity of the material, forms a compact interface, improves the stability of lithium silicon oxide, and reduces the side reaction of electrolyte. The material prepared by the invention has the advantages of strong water resistance, stable structure, high capacity, high coulomb efficiency, stable circulation and good application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the silicon-oxygen-carbon material obtained in example 1 at a magnification of 1.50K X.
Fig. 2 is a first charge-discharge curve of the silicon-oxygen-carbon material obtained in example 1.
FIG. 3 is a cycle curve of the silicon-oxygen-carbon material obtained in example 4.
Detailed Description
The technical solutions of the present invention will be clearly described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
In the following examples, the microtopography of the prepared samples was determined using a Hitachi S-3400N scanning electron microscope. The battery performance test was performed using a battery test system model LANHE CT2001A manufactured by marten blue electronic company, inc.
The silicon-oxygen-carbon negative electrode material, the conductive agent carbon black and the binder (PAA) are prepared into slurry according to the mass ratio of 8:1:1, and the slurry is uniformly coated on copper foil and dried to prepare the electrode. The electrolyte is 1.0 mol L -1 LiPF of (a) 6 The solvent is EC: DEC: DMC with a mass ratio of 1:1:1, and the additive is 10% FEC. The diaphragm is a microporous polypropylene diaphragm, the anode is a lithium sheet, and the CR2025 button cell is processed. The first-round discharge test was discharged to 0.005V with 100 mA/g and recharged to 2.0V. And carrying out constant-current charge and discharge test with 200mA/g for cycle performance test, wherein the charge and discharge voltage range is 0.005-2V, and the test is carried out at a constant temperature of 25 ℃.
Example 1
The preparation method of the simple pre-lithium metal doped silicon-oxygen-carbon anode material comprises the following steps:
(1) Preparing 200 mL of acetic acid aqueous solution with pH of 3, adding 2g of chitosan, and carrying out ultrasonic treatment and uniform stirring to obtain an acidic chitosan solution B;
(2) Adding 10g of silicon oxide into the solution B, simultaneously dropwise adding CNTs dispersion liquid (solid content is 0.4%) with CNTs content of 0.1g, and carrying out ultrasonic treatment and stirring uniformly to obtain a dispersion liquid D;
(3) Adding 0.5g of ferric chloride into the dispersion liquid D, uniformly stirring to obtain a dispersion liquid C, controlling the inlet temperature of spray drying to be 180 ℃, the outlet temperature to be 95 ℃ and the feeding speed to be 3 rad/min to obtain a precursor E;
(4) Adding 2g of phenolic resin into 200 mL absolute ethyl alcohol, simultaneously dropwise adding CNTs ethyl acetate dispersion liquid (solid content is 0.4%) with CNTs content of 0.1g, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid H;
(5) Adding the silicon oxide precursor E into the dispersion liquid H, simultaneously adding tetrahydrofuran solution with the content of hexamethyldisilazide lithium of 1g, uniformly stirring, and then performing spray drying, wherein the inlet temperature is controlled to be 150 ℃, the outlet temperature is controlled to be 95 ℃, and the feeding speed is controlled to be 5 rad/min, so as to obtain a silicon oxide precursor I;
(6) And (3) placing the silicon oxide precursor I into a tube furnace for inert atmosphere protection high-temperature sintering, firstly heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, then heating to 800 ℃ at a heating rate of 3 ℃/min, preserving heat for 2 hours, naturally cooling, and then crushing and sieving with a 300-mesh sieve to obtain the pre-lithium metal doped silicon oxide carbon anode material.
The obtained silicon-oxygen-carbon material is prepared into slurry, smeared and assembled into a lithium ion half battery, and the lithium ion half battery has good cycle and multiplying power performance when tested under the current density of 100 mA/g, and the initial charge specific capacity reaches 1258.6 mAh/g and the initial effect reaches 83.53%.
Example 2
The preparation method of the simple pre-lithium metal doped silicon-oxygen-carbon anode material comprises the following steps:
(1) Preparing 200 mL of citric acid aqueous solution with pH of 3, adding 1g of glucose, and carrying out ultrasonic treatment and uniform stirring to obtain an acidic glucose solution B;
(2) Adding 10g of silicon oxide into the solution B, simultaneously dropwise adding graphene dispersion liquid (solid content is 0.1%) with graphene content of 0.2g, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid D;
(3) Adding 0.1g of cobalt nitrate into the dispersion liquid D, uniformly stirring to obtain a dispersion liquid C, controlling the inlet temperature of spray drying to 140 ℃, the outlet temperature to 90 ℃ and the feeding speed to 5 rad/min to obtain a precursor E;
(4) Adding 2g of acrylic resin into 200 mL anhydrous methanol, simultaneously dropwise adding CNTs methanol dispersion liquid (solid content is 0.1%) with CNTs content of 0.1g, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid H;
(5) Adding the silicon oxide precursor E into the dispersion liquid H, simultaneously adding tetrahydrofuran solution with the content of lithium tri-sec-butylborohydride of 1g, uniformly stirring, and then performing spray drying, wherein the inlet temperature is controlled to be 160 ℃, the outlet temperature is controlled to be 95 ℃, and the feeding speed is 6 rad/min to obtain a silicon oxide precursor I;
(6) And (3) placing the silicon oxide precursor I into a tube furnace for inert atmosphere protection high-temperature sintering, firstly heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, then heating to 700 ℃ at a heating rate of 3 ℃/min, preserving heat for 3 hours, naturally cooling, and then crushing and sieving with a 300-mesh sieve to obtain the pre-lithium metal doped silicon oxide carbon anode material.
The obtained silicon-oxygen-carbon material is prepared into slurry, smeared and assembled into a lithium ion half battery, and the lithium ion half battery has good circulation and multiplying power performance when tested under the current density of 100 mA/g, and the first charge specific capacity reaches 1187.5 mAh/g and the first effect is 82.52%.
Example 3
The preparation method of the simple pre-lithium metal doped silicon-oxygen-carbon anode material comprises the following steps:
(1) Preparing 200 mL of hydrochloric acid aqueous solution with the PH of 3, adding 3g of sucrose, and carrying out ultrasonic treatment and uniform stirring to obtain an acidic sucrose solution B;
(2) Adding 10g of silicon oxide into the solution B, simultaneously dropwise adding conductive fiber dispersion liquid (solid content is 2%) with the conductive fiber content of 0.2g, and obtaining a dispersion liquid D after ultrasonic treatment and uniform stirring;
(3) Adding 0.2g of calcium citrate into the dispersion liquid D, uniformly stirring to obtain a dispersion liquid C, controlling the inlet temperature of spray drying to be 200 ℃, the outlet temperature to be 110 ℃ and the feeding speed to be 12 rad/min to obtain a precursor E;
(4) Adding 2g of polyethylene glycol into 200 mL anhydrous ethylene glycol, simultaneously dropwise adding conductive fiber ethylene glycol dispersion liquid (solid content is 2%) with conductive fiber content of 0.2g, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid H;
(5) Adding the silicon oxide precursor E into the dispersion liquid H, simultaneously adding a tetrahydrofuran solution with the content of lithium triethylborohydride of 1g, uniformly stirring, and then performing spray drying, wherein the inlet temperature is controlled to be 170 ℃, the outlet temperature is controlled to be 100 ℃, and the feeding speed is controlled to be 12 rad/min, so as to obtain a silicon oxide precursor I;
(6) And (3) placing the silicon oxide precursor I into a tube furnace for inert atmosphere protection high-temperature sintering, heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 2 hours, naturally cooling, crushing, and sieving with a 300-mesh sieve to obtain the pre-lithium metal doped silicon oxide carbon negative electrode material.
The obtained silicon-oxygen-carbon material is prepared into slurry, smeared and assembled into a lithium ion half battery, and the lithium ion half battery has good cycle and multiplying power performance when tested under the current density of 100 mA/g, and the first charge specific capacity reaches 1212.0 mAh/g and the first effect reaches 80.21%.
Example 4
The preparation method of the simple pre-lithium metal doped silicon-oxygen-carbon anode material comprises the following steps:
(1) Preparing 200 mL of sulfuric acid aqueous solution with the PH of 3, adding 2g of polyvinyl alcohol, and carrying out ultrasonic treatment and uniform stirring to obtain an acidic polyvinyl alcohol solution B;
(2) Adding 10g of silicon oxide into the solution B, simultaneously dropwise adding CNTs dispersion liquid (solid content is 1%) with CNTs content of 0.2g, and obtaining a dispersion liquid D after ultrasonic treatment and uniform stirring;
(3) Adding 0.5g of nickel acetate into the dispersion liquid D, uniformly stirring to obtain a dispersion liquid C, controlling the inlet temperature of spray drying to be 150 ℃, the outlet temperature to be 95 ℃ and the feeding speed to be 10 rad/min to obtain a precursor E;
(4) Adding 1g of polyvinylpyrrolidone into 200 mL anhydrous isopropanol, simultaneously dropwise adding CNTs isopropanol dispersion liquid (solid content is 1%) with CNTs content of 0.1g, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid H;
(5) Adding the silicon oxide precursor E into the dispersion liquid H, simultaneously adding tetrahydrofuran solution with the content of hexamethyldisilazide lithium of 1.5g, uniformly stirring, and then performing spray drying, wherein the inlet temperature is controlled to be 180 ℃, the outlet temperature is controlled to be 100 ℃, and the feeding speed is controlled to be 10 rad/min, so as to obtain a silicon oxide precursor I;
(6) And (3) placing the silicon oxide precursor I into a tube furnace for inert atmosphere protection high-temperature sintering, firstly heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, then heating to 1000 ℃ at a heating rate of 3 ℃/min, preserving heat for 2 hours, naturally cooling, and then crushing and sieving with a 300-mesh sieve to obtain the pre-lithium metal doped silicon oxide carbon anode material.
The obtained silicon-oxygen-carbon material is prepared into slurry, smeared and assembled into a lithium ion half battery, and the lithium ion half battery has good cycle and multiplying power performance when tested under the current density of 100 mA/g, and the first charge specific capacity reaches 1512.0 mAh/g and the first effect reaches 80.42%.
Example 5
The preparation method of the simple pre-lithium metal doped silicon-oxygen-carbon anode material comprises the following steps:
(1) Preparing 200 mL of phytic acid aqueous solution with the PH of 3, adding 2g of polyvinylpyrrolidone, carrying out ultrasonic treatment and stirring uniformly to obtain an acidic polyvinylpyrrolidone solution B;
(2) Adding 10g of silicon oxide into the solution B, simultaneously dropwise adding CNTs dispersion liquid (solid content is 1.5%) with CNTs content of 0.1g, and carrying out ultrasonic treatment and stirring uniformly to obtain a dispersion liquid D;
(3) Adding 0.4g of calcium chloride into the dispersion liquid D, uniformly stirring to obtain a dispersion liquid C, controlling the inlet temperature of spray drying to be 180 ℃, the outlet temperature to be 95 ℃ and the feeding speed to be 4 rad/min to obtain a precursor E;
(4) Adding 2g of cellulose into 200 mL anhydrous ethyl acetate, simultaneously dropwise adding CNTs ethyl acetate dispersion liquid (solid content is 1.5%) with CNTs content of 0.1g, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid H;
(5) Adding the silicon oxide precursor E into the dispersion liquid H, adding tetrahydrofuran solution with the content of lithium tri-sec-butylborohydride of 1.5g, uniformly stirring, and then performing spray drying, wherein the inlet temperature is controlled to be 190 ℃, the outlet temperature is controlled to be 105 ℃, and the feeding speed is controlled to be 12 rad/min, so as to obtain a silicon oxide precursor I;
(6) And (3) placing the silicon-oxygen precursor I into a tube furnace for inert atmosphere protection high-temperature sintering, firstly heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, then heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 1.5 hours, naturally cooling, crushing and sieving with a 300-mesh sieve to obtain the pre-lithium metal doped silicon-oxygen carbon anode material.
The obtained silicon-oxygen-carbon material is prepared into slurry, smeared and assembled into a lithium ion half battery, and the lithium ion half battery has good cycle and multiplying power performance when tested under the current density of 100 mA/g, and the first charge specific capacity reaches 1112.8 mAh/g and the first effect reaches 83.25%.
Example 6
The preparation method of the simple pre-lithium metal doped silicon-oxygen-carbon anode material comprises the following steps:
(1) Preparing 200 mL of acetic acid aqueous solution with the PH of 3, adding 2g of sodium alginate, and carrying out ultrasonic treatment and uniform stirring to obtain an acidic sodium alginate solution B;
(2) Adding 10g of silicon oxide into the solution B, simultaneously dropwise adding graphene dispersion liquid (solid content is 0.5%) with graphene content of 0.05g, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid D;
(3) Adding 0.5g of ferric chloride into the dispersion liquid D, uniformly stirring to obtain a dispersion liquid C, controlling the inlet temperature of spray drying to be 200 ℃, the outlet temperature to be 105 ℃ and the feeding speed to be 8rad/min to obtain a precursor E;
(4) Adding 2g of sodium alginate into 200 mL anhydrous azotemic dimethylformamide, simultaneously dropwise adding graphene azotemic dimethylformamide dispersion liquid (solid content is 0.5%) with CNTs content of 0.05g, and carrying out ultrasonic treatment and stirring uniformly to obtain a dispersion liquid H;
(5) Adding the silicon oxide precursor E into the dispersion liquid H, simultaneously adding a tetrahydrofuran solution with the content of lithium triethylborohydride of 2g, uniformly stirring, and then performing spray drying, wherein the inlet temperature is controlled to be 160 ℃, the outlet temperature is controlled to be 90 ℃, and the feeding speed is 5 rad/min to obtain a silicon oxide precursor I;
(6) And (3) placing the silicon oxide precursor I into a tube furnace for inert atmosphere protection high-temperature sintering, firstly heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, then heating to 1000 ℃ at a heating rate of 3 ℃/min, preserving heat for 2 hours, naturally cooling, and then crushing and sieving with a 300-mesh sieve to obtain the pre-lithium metal doped silicon oxide carbon anode material.
The obtained silicon-oxygen-carbon material is prepared into slurry, smeared and assembled into a lithium ion half battery, and the lithium ion half battery has good cycle and multiplying power performance when tested under the current density of 100 mA/g, and the first charge specific capacity reaches 1124.0 mAh/g and the first effect reaches 83.26%.
Example 7
The preparation method of the simple pre-lithium metal doped silicon-oxygen-carbon anode material comprises the following steps:
(1) Preparing 200 mL of citric acid aqueous solution with pH of 3, adding 2g of chitosan, and carrying out ultrasonic treatment and uniform stirring to obtain an acidic chitosan solution B;
(2) Adding 10g of silicon oxide into the solution B, simultaneously dropwise adding conductive fiber dispersion liquid (solid content is 1%) with the conductive fiber content of 0.3g, and obtaining a dispersion liquid D after ultrasonic treatment and uniform stirring;
(3) Adding 0.2g of nickel citrate into the dispersion liquid D, uniformly stirring to obtain a dispersion liquid C, controlling the inlet temperature of spray drying to 190 ℃, the outlet temperature to 100 ℃ and the feeding speed to 6 rad/min to obtain a precursor E;
(4) Adding 2g of citric acid into 200 mL absolute ethyl alcohol, simultaneously dropwise adding conductive fiber ethyl acetate dispersion liquid (solid content is 1%) with the conductive fiber content of 0.2g, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid H;
(5) Adding the silicon oxide precursor E into the dispersion liquid H, simultaneously adding tetrahydrofuran solution with the content of hexamethyldisilazide lithium of 2g, uniformly stirring, and then performing spray drying, wherein the inlet temperature is controlled to be 180 ℃, the outlet temperature is controlled to be 100 ℃, and the feeding speed is 6 rad/min to obtain a silicon oxide precursor I;
(6) And (3) placing the silicon oxide precursor I into a tube furnace for inert atmosphere protection high-temperature sintering, heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 2 hours, naturally cooling, crushing, and sieving with a 300-mesh sieve to obtain the pre-lithium metal doped silicon oxide carbon negative electrode material.
The obtained silicon-oxygen-carbon material is prepared into slurry, smeared and assembled into a lithium ion half battery, and the lithium ion half battery has good cycle and multiplying power performance when tested under the current density of 100 mA/g, and the first charge specific capacity reaches 1058.6 mAh/g and the first effect reaches 83.12%.
Example 8
The preparation method of the simple pre-lithium metal doped silicon-oxygen-carbon anode material comprises the following steps:
(1) Preparing 200 mL of hydrochloric acid aqueous solution with the PH of 3, adding 4g of sucrose, and carrying out ultrasonic treatment and uniform stirring to obtain an acidic sucrose solution B;
(2) Adding 10g of silicon oxide into the solution B, simultaneously dropwise adding CNTs dispersion liquid (solid content is 0.8%) with CNTs content of 0.5g, and obtaining a dispersion liquid D after ultrasonic treatment and uniform stirring;
(3) Adding 0.8g of zinc acetate into the dispersion liquid D, uniformly stirring to obtain a dispersion liquid C, controlling the inlet temperature of spray drying to be 180 ℃, the outlet temperature to be 100 ℃ and the feeding speed to be 5 rad/min to obtain a precursor E;
(4) Adding 0.5g of stearic acid into 200 mL anhydrous glycol, simultaneously dropwise adding CNTs glycol dispersion liquid (solid content is 0.8%) with CNTs content of 0.5g, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid H;
(5) Adding the silicon oxide precursor E into the dispersion liquid H, simultaneously adding tetrahydrofuran solution with the content of lithium tri-sec-butylborohydride of 1.6g, uniformly stirring, and then performing spray drying, wherein the inlet temperature is controlled to be 190 ℃, the outlet temperature is controlled to be 100 ℃, and the feeding speed is 8rad/min to obtain a silicon oxide precursor I;
(6) And (3) placing the silicon oxide precursor I into a tube furnace for inert atmosphere protection high-temperature sintering, firstly heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, then heating to 1000 ℃ at a heating rate of 3 ℃/min, preserving heat for 1 hour, naturally cooling, and then crushing and sieving with a 300-mesh sieve to obtain the pre-lithium metal doped silicon oxide carbon anode material.
The obtained silicon-oxygen-carbon material is prepared into slurry, smeared and assembled into a lithium ion half battery, and the lithium ion half battery has good cycle and multiplying power performance when tested under the current density of 100 mA/g, and the first charge specific capacity reaches 1146.5 mAh/g and the first effect reaches 83.36%.
The foregoing description of the preferred embodiments of the present invention is not intended to be limiting, but rather, it is intended to cover all modifications, adaptations, and the like as fall within the spirit of the present invention.

Claims (10)

1. A simple pre-lithium metal doped silicon oxygen carbon negative electrode material is characterized in that: the negative electrode material comprises silicon oxide, wherein the silicon oxide is coated with a first modified carbon layer, the first modified carbon layer is coated with a second modified carbon layer, and the first modified carbon layer contains metal active substances and conductive carbon; the second modified carbon layer contains an active pre-lithium agent and conductive carbon, and the active pre-lithium agent and conductive carbonThe reaction of the silicon oxide forms a layer of Li on the surface 2 SiO 3 And a layer, wherein the first modified carbon layer and the second modified carbon layer together form a multi-stage coating layer on the surface of the silicon oxide.
2. The simple pre-lithium metal doped silicon oxygen carbon negative electrode material according to claim 1, wherein: the silica particle size is 3-5 μm, wherein the silica ratio=0.9-1.1; the mass content of the silicon oxide is 70-95%, the mass content of the first modified carbon layer is 0.1-10%, the mass content of the second modified carbon layer is 0.1-10%, the mass content of the total conductive carbon is 0.5-2%, the mass content of the metal active substance is 0.1-5%, and the molar ratio of the silicon oxide to the active pre-lithium agent is 20:1-6:1.
3. The method for preparing the simple pre-lithium metal doped silicon oxygen carbon anode material according to claim 1, which is characterized in that: the simple pre-lithium metal doped silicon-oxygen-carbon negative electrode material is prepared through two different spray drying and one sintering processes, a first carbon coating layer is formed on the surface of silicon oxide through one spray drying, and a metal active substance is introduced at the same time; the secondary uniform coating of the surface is realized through the secondary spray drying, and meanwhile, an active pre-lithium agent is introduced; the carbon source is coated twice in the sintering process to form a first modified carbon layer and a second modified carbon layer, and simultaneously the active pre-lithium agent reacts with the silicon oxide to form a layer of Li on the surface 2 SiO 3 And a layer, wherein the first modified carbon layer and the second modified carbon layer together form a multi-stage coating layer on the surface of the silicon oxide.
4. The method for preparing the simple pre-lithium metal doped silicon oxygen carbon anode material according to claim 3, which is characterized by comprising the following specific preparation processes:
(1) Preparing an acidic aqueous solution with the pH of 3, adding a carbon source A, carrying out ultrasonic treatment and uniformly stirring to obtain an aqueous solution B;
(2) Adding silicon oxide into the aqueous solution B, simultaneously dropwise adding the conductive carbon aqueous solution C, and carrying out ultrasonic treatment and uniform stirring to obtain a dispersion liquid D;
(3) Adding metal salt M into the dispersion D, stirring uniformly to obtain a dispersion C, and spray-drying to obtain a silicon-oxygen-carbon precursor E;
(4) Adding a carbon source F into an anhydrous organic solvent, simultaneously dropwise adding a conductive carbon solution G, performing ultrasonic treatment and uniformly stirring to obtain a dispersion liquid H;
(5) Adding the silicon oxide precursor E into the dispersion liquid H, adding an active pre-lithium agent solution, uniformly stirring, and then performing spray drying to obtain a silicon oxide precursor I;
(6) And (3) placing the silicon oxide precursor I into a tube furnace for inert atmosphere protection high-temperature sintering, cooling, crushing and sieving with a 300-mesh sieve to obtain the pre-lithium metal doped silicon oxide carbon negative electrode material.
5. The method for preparing the simple pre-lithium metal doped silicon oxygen carbon anode material according to claim 4, which is characterized in that: the acid in the acidic aqueous solution in the step (1) is citric acid, acetic acid, hydrochloric acid, sulfuric acid or phytic acid; the carbon source A is one or more of chitosan, glucose, sucrose, polyvinyl alcohol, polyvinylpyrrolidone or sodium alginate.
6. The method for preparing the simple pre-lithium metal doped silicon oxygen carbon anode material according to claim 4, which is characterized in that: the conductive carbon in the step (2) and the step (4) is one of carbon nanotubes, graphene or conductive fibers, and the solid content is 0.1-2%, preferably 0.4-1%; wherein the conductive carbon solution G in the step (4) adopts one of ethanol, methanol, ethylene glycol, ethyl acetate and azomethine formamide.
7. The method for preparing the simple pre-lithium metal doped silicon oxygen carbon anode material according to claim 4, which is characterized in that: the metal salt M in the step (3) is Fe, co, ni, mg, ca or Zn chloride, nitrate, citrate or acetate; the anhydrous organic solvent in the step (4) is ethanol, methanol, glycol, isopropanol, ethyl acetate or azomethine formamide; the carbon source F in the step (4) is phenolic resin, acrylic resin, polyethylene glycol, polyvinylpyrrolidone, cellulose, polystyrene, citric acid or stearic acid.
8. The method for preparing the simple pre-lithium metal doped silicon oxygen carbon anode material according to claim 4, which is characterized in that: the active pre-lithium agent solution in the step (5) is tetrahydrofuran solution of hexamethyldisilazane lithium amide, tri-sec-butyl lithium borohydride or triethyl lithium borohydride, and the concentration of the active pre-lithium agent solution is 1M.
9. The method for preparing the simple pre-lithium metal doped silicon oxygen carbon anode material according to claim 4, which is characterized in that: the spray drying inlet temperature in the step (3) is 140-200 ℃, the outlet temperature is 90-110 ℃, the feeding speed is 3-12 rad/min, the air atmosphere is in a spraying pressure of 0.2MPa; the spray drying inlet temperature in the step (5) is 150-190 ℃, the outlet temperature is 90-110 ℃, the feeding speed is 5-12 rad/min, and the nitrogen atmosphere is adopted.
10. The method for preparing the simple pre-lithium metal doped silicon oxygen carbon anode material according to claim 4, which is characterized in that: the sintering condition in the step (6) is two-stage sintering: heating to 250 ℃ at normal temperature, wherein the heating rate is 5 ℃/min, and preserving heat for 2 hours; heating to 700-1000 deg.C at 3 deg.C/min, maintaining for 2-4 hr, naturally cooling, and using high purity argon with purity of 99.999% as shielding gas.
CN202211556745.7A 2022-12-06 2022-12-06 Simple pre-lithium metal doped silicon oxygen carbon negative electrode material and preparation method thereof Pending CN116093300A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117438554A (en) * 2023-10-11 2024-01-23 银硅(宁波)科技有限公司 High-first-efficiency silicon oxide negative electrode material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117438554A (en) * 2023-10-11 2024-01-23 银硅(宁波)科技有限公司 High-first-efficiency silicon oxide negative electrode material and preparation method thereof
CN117438554B (en) * 2023-10-11 2024-04-23 银硅(宁波)科技有限公司 High-first-efficiency silicon oxide negative electrode material and preparation method thereof

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