CN104377351A - Si-C-N composite negative pole material and preparation method thereof - Google Patents
Si-C-N composite negative pole material and preparation method thereof Download PDFInfo
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- CN104377351A CN104377351A CN201410515321.5A CN201410515321A CN104377351A CN 104377351 A CN104377351 A CN 104377351A CN 201410515321 A CN201410515321 A CN 201410515321A CN 104377351 A CN104377351 A CN 104377351A
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- H01M4/02—Electrodes composed of, or comprising, active material
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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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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a Si-C-N composite negative pole material and a preparation method thereof and belongs to the field of lithium ion battery negative pole materials. The preparation method comprises the following steps of heating a mixture of a Si source and an N source to a temperature of 600-1000 DEG C at a heating rate of 0.5-10 DEG C/min in an Ar atmosphere, carrying out sintering at a temperature of 600-1000 DEG C for 3-15h, carrying out cooling to a room temperature to obtain an N-doped Si-based material, mixing the N-doped Si-based material and graphite to obtain a uniform mixture, heating the mixture of the N-doped Si-based material and graphite to a temperature of 500-900 DEG C at a heating rate of 0.5-10 DEG C/min in an N atmosphere, carrying out sintering at a temperature of 500-900 DEG C for 1-10h, and carrying out cooling to a room temperature to obtain the Si-C-N composite negative pole material. Through use of N in the Si material, Si material bandwidth is reduced and conductivity is improved. Through coating of the N-doped Si-based material with graphite, volume effects of the Si material is effectively buffered. The Si-C-N composite negative pole material has excellent multiplying power performances and cycle stability.
Description
Technical field
The present invention relates to lithium ion battery negative material field, particularly a kind of silico-carbo-nitrogen composite negative pole material and preparation method thereof.
Background technology
Lithium battery (i.e. lithium ion battery) be a kind of with carbon element active material for negative pole, can the battery of discharge and recharge with what make positive pole containing the compound of lithium.Its charge and discharge process, is embedding and the deintercalation process of lithium ion: during charging, and lithium ion is from positive pole deintercalation, and by electrolyte and barrier film, embed negative pole, the lithium ion embedded in negative pole is more, and the charge specific capacity of battery is higher; Otherwise during electric discharge, lithium ion is from negative pole deintercalation, and by electrolyte and barrier film, embed positive pole, from negative pole, the lithium ion of deintercalation is more, and the specific discharge capacity of battery is higher.Visible, the charge-discharge performance of embedding lithium capacity (i.e. specific capacity) on battery of lithium cell cathode material has important impact.At present, the lithium ion battery of commercial applications extensively adopts graphite and modified graphite as negative material.Graphitic conductive is good, there is layer structure, the embedding of very applicable lithium ion and deintercalation (embedding lithium coefficient of cubical expansion < 9%), show higher coulombic efficiency and good cyclical stability, but its theoretical maximum specific capacity is lower, be only 372 mAh/g, which has limited the further raising of lithium ion battery specific energy.
Silica-base material has height ratio capacity, up to 4200 mAh/g, is counted as a kind of promising negative material.But in the embedding of lithium ion and the process of deintercalation, silica-base material exists and has very large bulk effect (cubical expansivity is up to 300%-400%), to cause in charging and discharging lithium battery process due to the efflorescence of silica-base material and come off, affect the connection between active material and collector on the one hand, be unfavorable for electric transmission; Make solid electrolyte interface film (the solid electrolyte interface formed between silica-base material and electrolyte on the other hand, be called for short SEI) film progressive additive, be unfavorable for improving lithium battery capacity, cause the cycle performance of lithium battery sharply to decline.Therefore, be necessary to cushion the bulk effect of silica-base material.
Prior art (CN 102593418 A) prepares carbon silicon composite cathode material by carbon and silicon are carried out compound, make to have the carbon of relative resilient structure and this space to cushion the bulk effect of silicon, improve the cycle performance of silicon, its step is as follows: (1) mixes: mixed with silica flour by organic carbon presoma, obtain the mixture of organic carbon presoma and silica flour; (2) coated: by said mixture high temperature cabonization in an inert atmosphere, to obtain the composite material of the tight coated Si of porous carbon layer; (3) corrode: remove the part silicon in the composite material of the tight coated Si of described porous carbon layer with corrosive liquid, obtain carbon silicon composite cathode material, in this carbon silicon composite cathode material, between carbon and silicon, there is space.
Inventor finds that prior art at least exists following problem:
The cyclical stability of the negative material that prior art provides and high rate performance poor.
Summary of the invention
Embodiment of the present invention technical problem to be solved is, provides a kind of cyclical stability and high rate performance preferably silico-carbo-nitrogen composite negative pole material and preparation method thereof.Concrete technical scheme is as follows:
First aspect, embodiments provides the preparation method of a kind of silico-carbo-nitrogen composite negative pole material, comprising:
Step a, under an argon atmosphere, with the heating rate of 0.5-10 DEG C/min, the mixture of silicon source and nitrogenous source is heated to 600-1000 DEG C, and sinters 3-15 hour at the temperature of 600-1000 DEG C, be then cooled to room temperature, obtain the silica-base material of nitrating;
Step b, the silica-base material of described nitrating and graphite to be mixed, and in a nitrogen atmosphere, with the heating rate of 0.5-10 DEG C/min, the mixture of the silica-base material of described nitrating and described graphite is heated to 500-900 DEG C, and 1-10 hour is sintered at the temperature of 500-900 DEG C, then be cooled to room temperature, obtain silico-carbo-nitrogen composite negative pole material.
Particularly, as preferably, in described step a, in the silica-base material of described nitrating, the mass fraction of nitrogen is 0.2%-8%.
Particularly, in described step a, described silicon source is selected from least one in nano silica fume, silicon monoxide, esters of silicon acis, silicon alloy.
Particularly, described esters of silicon acis is tetraethoxysilane and/or methyl silicate.
Particularly, described silicon alloy is silicon-aluminum, silicon copper, silicon silver alloy or silicomangan.
Particularly, as preferably, in described step a, described nitrogenous source is organic amine and/or inorganic ammonium salt.
Particularly, described organic amine is selected from least one in ethylenediamine, antifebrin, acetamide, diacetayl amide, diacetyl ethamine, diacetyl methylamine, diacetanilide, dimethylamine, diphenylamines, triethylamine, trimethylamine, triphenylamine.
Particularly, described inorganic ammonium salt is selected from (NH
4)
2cO
3, NH
4hCO
3, NH
4nO
3, (NH
4)
2sO
4, NH
4hSO
4, (NH
4)
3pO
4, (NH
4)
2hPO
4, NH
4h
2pO
4in at least one.
Particularly, as preferably, in described step b, the silica-base material of described nitrating and the mass ratio of described graphite are 0.02-5:1.
As preferably, described graphite is that coulombic efficiency is more than or equal to the Delanium of 92% first.
Second aspect, embodiments provides a kind of silico-carbo-nitrogen composite negative pole material utilizing above-mentioned any one method to prepare.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
The preparation method of the silico-carbo that the embodiment of the present invention provides-nitrogen composite negative pole material, by sintering the mixture in silicon source and nitrogenous source, carrying out N doping to silicon materials, can reduce the bandwidth of silicon materials, improve its conductivity.Then the silica-base material of the nitrating obtained and the mixture of graphite are sintered again in a nitrogen atmosphere, make graphite coat on the silica-base material surface of this nitrating, effectively can not only cushion the bulk effect of silicon materials, and nitrogen can replace part carbon atom or active oxygen, thus the silico-carbo-nitrogen composite negative pole material prepared is made to have excellent high rate performance and cyclical stability.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the first charge-discharge cycle performance curve chart of the lithium ion battery that the embodiment of the present invention 6 provides;
Fig. 2 is that lithium ion battery that the embodiment of the present invention 6 provides circulates the discharge cycles performance chart of 100 times;
Fig. 3 is the discharge cycles performance chart of lithium ion battery under different charge-discharge magnification that the embodiment of the present invention 6 provides.
Embodiment
For making technical scheme of the present invention and advantage clearly, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
First aspect, embodiments provides the preparation method of a kind of silico-carbo-nitrogen composite negative pole material, comprising:
Step 101, under an argon atmosphere, with the heating rate of 0.5-10 DEG C/min, the mixture of silicon source and nitrogenous source is heated to 600-1000 DEG C, and sinters 3-15 hour at the temperature of 600-1000 DEG C, be then cooled to room temperature, obtain the silica-base material of nitrating.
The embodiment of the present invention, by sintering the mixture of silicon source and nitrogenous source under an argon atmosphere, makes nitrogen-doping in silicon materials, forms the silica-base material of nitrating.Owing to having carried out N doping to silicon materials, the bandwidth of silicon materials can be reduced, effectively improve the electric conductivity of silicon materials, and then be beneficial to the cyclical stability of prepared negative material and the raising of high rate performance.
Particularly, in order to ensure that the electric conductivity of silica-base material is able to effective raising, and do not affect the higher specific capacity of silica-base material itself, in the silica-base material of above-mentioned nitrating, the mass fraction of nitrogen is 0.2%-8%.
Particularly, above-mentioned silicon source is selected from least one in nano silica fume, silicon monoxide, esters of silicon acis, silicon alloy.
For example, above-mentioned nano silica fume can be the high-purity silicon powder of 5-80nm for particle diameter.Above-mentioned esters of silicon acis can be tetraethoxysilane and/or methyl silicate.Above-mentioned silicon alloy can be silicon-aluminum, silicon copper, silicon silver alloy or silicomangan etc.
For example, above-mentioned nitrogenous source is organic amine and/or inorganic ammonium salt.Such as, above-mentioned organic amine can be selected from least one in ethylenediamine, antifebrin, acetamide, diacetayl amide, diacetyl ethamine, diacetyl methylamine, diacetanilide, dimethylamine, diphenylamines, triethylamine, trimethylamine, triphenylamine.Above-mentioned inorganic ammonium salt is selected from (NH
4)
2cO
3, NH
4hCO
3, NH
4nO
3, (NH
4)
2sO
4, NH
4hSO
4, (NH
4)
3pO
4, (NH
4)
2hPO
4, NH
4h
2pO
4in at least one.
Be understandable that, " room temperature " described in the embodiment of the present invention refers to normal temperature environment temperature well known in the art, and such as this room temperature can between 23-28 DEG C.
Step 102, the silica-base material of nitrating step 101 obtained and graphite mix, and in a nitrogen atmosphere, with the heating rate of 0.5-10 DEG C/min, the silica-base material of nitrating and the mixture of graphite are heated to 500-900 DEG C, and 1-10 hour is sintered at the temperature of 500-900 DEG C, then be cooled to room temperature, obtain silico-carbo-nitrogen composite negative pole material.
The embodiment of the present invention, by a nitrogen atmosphere, sinters the silica-base material of nitrating and the mixture of graphite, makes graphite coat on the silica-base material surface of nitrating.Due to graphite doff lithium volumetric expansion in charge and discharge process less (the embedding lithium coefficient of cubical expansion is less than 9%), and it is layer structure, good conductivity, can removal lithium embedded fast, improves the cyclical stability of negative material.By sintering in a nitrogen atmosphere, nitrogen can replace part carbon atom or active oxygen, can improve electric conductivity and the coulombic efficiency first of negative material further, show excellent cycle performance and high rate performance.
Due to Delanium coulombic efficiency is high first, specific discharge capacity is high, in charge and discharge process volumetric expansion little.As preferably, in the embodiment of the present invention, above-mentioned graphite is Delanium, and more preferably coulombic efficiency is more than or equal to the Delanium of 92% first.Further, also preferably coulombic efficiency is more than or equal to 92% and specific discharge capacity when 0.1C is more than or equal to the Delanium of 300mAh/g first.
In order to ensure that graphite evenly and completely can be coated on the silica-base material surface of nitrating, form the thin graphite linings of ideal thickness, in step 102, the silica-base material of nitrating and the mass ratio of graphite are 0.02-5:1, are preferably 1-4:1.
Second aspect, embodiments provides a kind of silico-carbo-nitrogen composite negative pole material utilizing above-mentioned any one method to prepare.
Be understandable that, the silico-carbo that the embodiment of the present invention prepares-nitrogen composite negative pole material at least comprises silicon, carbon, the simple substance of nitrogen or chemical composition.That is this negative material comprises the silica-base material of N doping and is coated on the graphite on silica-base material surface of this N doping.
Preferably, the median particle diameter (D50) of silico-carbo-nitrogen composite negative pole material that the embodiment of the present invention provides is 2-25 micron.
Below further the present invention will be described by specific embodiment.
Delanium used in following examples is all purchased from Qingdao Chen Yang graphite Co., Ltd, and the coulombic efficiency first of this Delanium is all greater than 92%, and the specific discharge capacity when 0.1C is greater than 300mAh/g.
Embodiment 1
Prepare the silica-base material of nitrating:
Silicon monoxide and ethylenediamine are mixed, then under an argon atmosphere, with 3 DEG C/min heating rate, the mixture of silicon monoxide and ethylenediamine is heated to 800 DEG C, and sinter 7 hours at such a temperature.Then be cooled to room temperature, obtain the silica-base material of nitrating.Wherein, in the silica-base material of this nitrating, the mass fraction of nitrogen is 4%.
Silica-base material Surface coating Delanium at nitrating:
According to mass ratio: the silica-base material of nitrating: Delanium=2:11, the silica-base material of nitrating and Delanium are mixed, and in a nitrogen atmosphere, with 5 DEG C/min heating rate, the silica-base material of nitrating and the mixture of Delanium are heated to 650 DEG C, and sinter 6 hours at such a temperature.Then be cooled to room temperature, namely obtain silico-carbo-nitrogen composite negative pole material that the present embodiment is expected.The median particle diameter recording this silico-carbo-nitrogen composite negative pole material is 5um.
Embodiment 2
Prepare the silica-base material of nitrating:
Tetraethoxysilane and acetamide are mixed, then under an argon atmosphere, with 1 DEG C/min heating rate, the mixture of silicon monoxide and ethylenediamine is heated to 650 DEG C, and sinter 5 hours at such a temperature.Then be cooled to room temperature, obtain the silica-base material of nitrating.Wherein, in the silica-base material of this nitrating, the mass fraction of nitrogen is 0.5%.
Silica-base material Surface coating Delanium at nitrating:
According to mass ratio: the silica-base material of nitrating: Delanium=4:1, the silica-base material of nitrating and Delanium are mixed, and in a nitrogen atmosphere, with 5 DEG C/min heating rate, the silica-base material of nitrating and the mixture of Delanium are heated to 700 DEG C, and sinter 8 hours at such a temperature.Then be cooled to room temperature, namely obtain silico-carbo-nitrogen composite negative pole material that the present embodiment is expected, and the median particle diameter recording this silico-carbo-nitrogen composite negative pole material be 3.5um.
Embodiment 3
Prepare the silica-base material of nitrating:
By high-purity silicon powder (purity is greater than 99.999%, and particle diameter is 60nm) and (NH
4)
2cO
3mix, then under an argon atmosphere, with 8 DEG C/min heating rate, the mixture of silicon monoxide and ethylenediamine is heated to 750 DEG C, and sinter 10 hours at such a temperature.Then be cooled to room temperature, obtain the silica-base material of nitrating.Wherein, in the silica-base material of this nitrating, the mass fraction of nitrogen is 7.2%.
Silica-base material Surface coating Delanium at nitrating:
According to mass ratio: the silica-base material of nitrating: Delanium=1:20, the silica-base material of nitrating and Delanium are mixed, and in a nitrogen atmosphere, with 0.5 DEG C/min heating rate, the silica-base material of nitrating and the mixture of Delanium are heated to 550 DEG C, and sinter 4 hours at such a temperature.Then be cooled to room temperature, namely obtain silico-carbo-nitrogen composite negative pole material that the present embodiment is expected, and the median particle diameter recording this silico-carbo-nitrogen composite negative pole material be 21um.
Embodiment 4
Prepare the silica-base material of nitrating:
Silicon copper particle (particle diameter is 100nm) and diacetanilide are mixed, then under an argon atmosphere, with 4 DEG C/min heating rate, the mixture of silicon monoxide and ethylenediamine is heated to 850 DEG C, and sinter 6.5 hours at such a temperature.Then be cooled to room temperature, obtain the silica-base material of nitrating.Wherein, in the silica-base material of this nitrating, the mass fraction of nitrogen is 0.4%.
Silica-base material Surface coating Delanium at nitrating:
According to mass ratio: the silica-base material of nitrating: Delanium=1:30, the silica-base material of nitrating and Delanium are mixed, and in a nitrogen atmosphere, with 6 DEG C/min heating rate, the silica-base material of nitrating and the mixture of Delanium are heated to 900 DEG C, and sinter 1 hour at such a temperature.Then be cooled to room temperature, namely obtain silico-carbo-nitrogen composite negative pole material that the present embodiment is expected, and the median particle diameter recording this silico-carbo-nitrogen composite negative pole material be 10um.
Embodiment 5
Prepare the silica-base material of nitrating:
By silicon monoxide and NH
4nO
3mix, then under an argon atmosphere, with 10 DEG C/min heating rate, the mixture of silicon monoxide and ethylenediamine is heated to 1000 DEG C, and sinter 3.5 hours at such a temperature.Then be cooled to room temperature, obtain the silica-base material of nitrating.Wherein, in the silica-base material of this nitrating, the mass fraction of nitrogen is 7.5%.
Silica-base material Surface coating Delanium at nitrating:
According to mass ratio: the silica-base material of nitrating: Delanium=1:1, the silica-base material of nitrating and Delanium are mixed, and in a nitrogen atmosphere, with 7.5 DEG C/min heating rate, the silica-base material of nitrating and the mixture of Delanium are heated to 850 DEG C, and sinter 8 hours at such a temperature.Then be cooled to room temperature, namely obtain silico-carbo-nitrogen composite negative pole material that the present embodiment is expected, and the median particle diameter recording this silico-carbo-nitrogen composite negative pole material be 18um.
Embodiment 6
The silico-carbo that the present embodiment utilizes embodiment 1 to provide-nitrogen composite negative pole material prepares lithium ion battery, and tests the chemical property of this lithium ion battery.Wherein, the preparation method of this lithium ion battery is as follows: silico-carbo embodiment 1 provided-nitrogen composite negative pole material mixes according to mass ratio 8:1:1 with conductive agent acetylene black, binding agent PVDF (Kynoar), with NMP (1-Methyl-2-Pyrrolidone), this mixture is modulated into slurry, evenly be coated on Copper Foil, put into baking oven, dry 1h for 80-120 DEG C, taking-up is washed into pole piece, 85 DEG C of vacuumize 12 hours, carry out compressing tablet, 85 DEG C of vacuumize 12 hours, obtained experimental cell pole piece.Wherein the compacted density of this pole piece is 1.65g/cm
3.
Then be to electrode with lithium sheet, electrolyte is 1.0mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2325 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
Be 0.01-1.5V in discharge and recharge by voltage, charging and discharging currents is under the condition of 0.1C, and carry out charge and discharge cycles test to this battery, test result is as follows:
As shown in Figure 1, the first discharge specific capacity of this battery is 677.97mAh/g, and initial charge specific capacity is 599.749, and coulombic efficiency is 88.5% first.As shown in Figure 2, this circulating battery still remains on more than 578.53mAh/g 100 times.Visible, this battery table reveals good cyclical stability.
Under the following conditions high rate performance test is carried out to this battery: discharge and recharge is 0.01-1.5V by voltage, and charging and discharging currents is respectively 0.1C, 0.2C, 0.5C, 1C, each circulation 10 times, wherein, 1C=670mA/g.Test result is as follows: as shown in Figure 3, and the specific discharge capacity of this battery when 0.1C is 635mAh/g, and the specific discharge capacity when 1C is still at more than 533mAh/g.Visible, this battery table reveals good high rate performance.
Embodiment 7
The silico-carbo that the present embodiment utilizes embodiment 2-5 to provide respectively-nitrogen composite negative pole material prepares lithium ion battery, and tests the chemical property of prepared lithium ion battery respectively.The preparation method of lithium ion battery is all identical with embodiment 6 with electrochemical property test method.Wherein, the compacted density of the battery pole piece prepared by the silico-carbo utilizing embodiment 2-5 to provide-nitrogen composite negative pole material is respectively 1.55g/cm
3, 1.77g/cm
3, 1.72g/cm
3, 1.8g/cm
3.
Cyclical stability and the high rate performance test result of above-mentioned each prepared lithium ion battery are as shown in table 1:
The electrochemical property test table of table 1 lithium ion battery
As shown in Table 1, the lithium ion battery prepared by the negative material utilizing embodiment of the present invention 2-5 to provide all shows good cyclical stability and high rate performance.Visible, the preparation method of the silico-carbo that the embodiment of the present invention provides-nitrogen composite negative pole material has high power capacity for preparation, the negative material of high conductivity has great importance.And the lithium ion battery that the negative material utilizing the embodiment of the present invention to provide prepares has excellent cyclical stability and high rate performance, be beneficial to large-scale promotion application.The method technique that the embodiment of the present invention provides is simple, cost is lower, is convenient to large-scale industrial and produces.
The foregoing is only preferred embodiment of the present invention, not in order to limit the scope of the invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for silico-carbo-nitrogen composite negative pole material, comprising:
Step a, under an argon atmosphere, with the heating rate of 0.5-10 DEG C/min, the mixture of silicon source and nitrogenous source is heated to 600-1000 DEG C, and sinters 3-15 hour at the temperature of 600-1000 DEG C, be then cooled to room temperature, obtain the silica-base material of nitrating;
Step b, the silica-base material of described nitrating and graphite to be mixed, and in a nitrogen atmosphere, with the heating rate of 0.5-10 DEG C/min, the mixture of the silica-base material of described nitrating and described graphite is heated to 500-900 DEG C, and 1-10 hour is sintered at the temperature of 500-900 DEG C, then be cooled to room temperature, obtain silico-carbo-nitrogen composite negative pole material.
2. method according to claim 1, is characterized in that, in described step a, in the silica-base material of described nitrating, the mass fraction of nitrogen is 0.2%-8%.
3. method according to claim 1, is characterized in that, in described step a, described silicon source is selected from least one in nano silica fume, silicon monoxide, esters of silicon acis, silicon alloy.
4. method according to claim 3, is characterized in that, described esters of silicon acis is tetraethoxysilane and/or methyl silicate.
5. method according to claim 1, is characterized in that, in described step a, described nitrogenous source is organic amine and/or inorganic ammonium salt.
6. method according to claim 5, it is characterized in that, described organic amine is selected from least one in ethylenediamine, antifebrin, acetamide, diacetayl amide, diacetyl ethamine, diacetyl methylamine, diacetanilide, dimethylamine, diphenylamines, triethylamine, trimethylamine, triphenylamine.
7. method according to claim 6, is characterized in that, described inorganic ammonium salt is selected from (NH
4)
2cO
3, NH
4hCO
3, NH
4nO
3, (NH
4)
2sO
4, NH
4hSO
4, (NH
4)
3pO
4, (NH
4)
2hPO
4, NH
4h
2pO
4in at least one.
8. method according to claim 1, is characterized in that, in described step b, the silica-base material of described nitrating and the mass ratio of described graphite are 0.02-5:1.
9. the method according to any one of claim 1-8, is characterized in that, described graphite is that coulombic efficiency is more than or equal to the Delanium of 92% first.
10. the silico-carbo utilizing the method described in any one of claim 1-9 to prepare-nitrogen composite negative pole material.
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US11929498B2 (en) | 2017-10-27 | 2024-03-12 | Lg Energy Solution, Ltd. | Silicon-carbon complex and lithium secondary battery comprising the same |
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US11929498B2 (en) | 2017-10-27 | 2024-03-12 | Lg Energy Solution, Ltd. | Silicon-carbon complex and lithium secondary battery comprising the same |
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