CN105870423A - Preparation method of silicon-based negative electrode material for lithium ion battery - Google Patents

Preparation method of silicon-based negative electrode material for lithium ion battery Download PDF

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CN105870423A
CN105870423A CN201610385411.6A CN201610385411A CN105870423A CN 105870423 A CN105870423 A CN 105870423A CN 201610385411 A CN201610385411 A CN 201610385411A CN 105870423 A CN105870423 A CN 105870423A
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silicon
nickel
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lithium
carbon
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田东
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method of a silicon-based negative electrode material for a lithium ion battery. A core-shell structure inside the silicon-based negative electrode material of the lithium ion battery is formed by taking silicon powder as a core and a composite material formed by the alloy compound of silicon and metallic nickel as well as a nickel mixture as a shell layer, and the outer surface is covered by a carbon layer. According to the method, carbon formed in the organic resin pyrolysis process, a carbon thermal reduction method is adopted, the rate performance is improved effectively by the introduction of the alloy compound of silicon and metallic nickel and nickel, and the core-shell structure is used for effectively inhibiting the volume expansion of the silicon powder during the charging and discharging process. The form of a carbon cladding layer on the surface of the composite material is pyrolytic amorphous carbon; on the one hand, the direct contact between the silicon powder and the electrolyte is isolated, so that the formation of an unstable SEI film on the surface of the silicon powder can be effectively avoided; on the other hand, the electrical conductivity of the composite material is improved by the carbon layer on the surface, and meanwhile, the volume expansion of the silicon powder in the charging and discharging process is inhibited.

Description

A kind of preparation method of Silicon Based Anode Materials for Lithium-Ion Batteries
Technical field
The invention belongs to technical field of lithium ion battery negative, be specifically related to the preparation method of a kind of Silicon Based Anode Materials for Lithium-Ion Batteries.
Background technology
Lithium ion battery has high energy density with it and excellent cycle performance has been widely used in the portable electric appts such as notebook computer, mobile phone, medical science microelectronic device.But, if to be applied to more wide field the most large-scale fixed energies storage device and problem that electric automobile yet suffers from much needing to solve.These problems include how to increase lithium ion battery energy density, the coupling strengthened between set of cells, the safety reduced in the decay of capacity in cyclic process, raising work process further, widen normal working temperature scope, the reliability of reinforcing material, reduction production cost etc..Now, generally believe that in the industry the important breakthrough in terms of lithium ion battery is to reform electrode material and anolyte portion, target be find performance to be better than the substitute of current commercially use material and electrochemical process that substitute is occurred in the course of the work will with keep consistent in the lithium ion battery principle used at present.Therefore, the research to lithium ion battery negative material is necessary.
The most commercially use graphite negative electrodes material, has relatively low lithium embedding/deintercalation current potential, suitable reversible capacity and aboundresources, the advantage such as cheap, is more satisfactory lithium ion battery negative material.But its theoretical specific capacity only has 372mAh/g, thus limits the further raising of lithium ion battery specific energy, it is impossible to meet the demand of growing high-energy Portable power source.Meanwhile, when graphite is as negative material, during first charge-discharge, form one layer of solid electrolyte film (SEI) on its surface.Solid electrolyte film is the formation that react to each other such as electrolyte, negative material and lithium ion, irreversibly consumes lithium ion, is the main factor forming irreversible capacity；It two is during Lithium-ion embeding, electrolyte is easily embedded in during moving out altogether with it, electrolyte is reduced, the gaseous product generated causes graphite flake layer to peel off, especially in the electrolyte containing PC, graphite flake layer comes off new for formation interface, causes further SEI to be formed, irreversible capacity increases, and cyclical stability declines simultaneously.Material with carbon element still exists as lithium ion battery negative material that charge/discharge capacity is low, first cycle irreversible loss is big, solvent molecule intercalation altogether and the shortcoming such as preparation cost is high, these be also in terms of current Study on Li-ion batteries needed for the key issue that solves.
Silicon, as the negative material of lithium battery, causes concern very early, and its theoretical reversible capacity is 4400 mAh/g, is 11 times of material with carbon element.Studies have found that, when silica flour is as negative active core-shell material, in charge and discharge process, the change in volume of granule is very big, causes silicon grain efflorescence, and electrode cycle is excessively poor.Bulk effect due to silicon, research worker have employed the composite of various silicon, such as Si-Ni alloy, the materials such as SiCN/C ceramic composite, Ti-Si alloy, Si-TiN composite, Cu5Si alloy, Ca2Si alloy and CrSi2 alloy, or individually carry out produced with combination silicon carbon material with graphite, cycle performance has obtained certain improvement, but the most not ideal enough.Except the composite of employing silicon, research worker also attempts using nano-silicon to make silicon carbon material.As used the method for magnetron sputtering or chemical deposition deposit thin films of silicon on a current collector, using chemical gaseous phase to be deposited on graphite surface deposition Nano thin film, use nano Si-Ni alloy, use high-energy mechanical ball milling to make Si-C composite material or the silica flour that uses particle mean size to be 80 nanometers makes the method such as Si-C composite material, these methods can improve the cycle performance of silicon really to a certain extent, but the limitation improved, the cycle performance of material still can not meet needs.
Summary of the invention
For above technical problem, the invention discloses the preparation method of a kind of Silicon Based Anode Materials for Lithium-Ion Batteries, described Silicon Based Anode Materials for Lithium-Ion Batteries is the silicon based composite material with nucleocapsid structure, can effectively overcome pure silicon powder problem in cyclic process.
To this, the technical solution used in the present invention is: a kind of Silicon Based Anode Materials for Lithium-Ion Batteries, and described Silicon Based Anode Materials for Lithium-Ion Batteries is nucleocapsid structure, and described stratum nucleare is silicon, intermediate layer is silicon and the alloy cpd of metallic nickel and the mixture of nickel, and pyrolytic carbon is outermost layer.
Using this technical scheme, silicon to effectively raise high rate performance with the alloy cpd of metallic nickel and the introducing of nickel, it effectively inhibits the volumetric expansion in silica flour charge and discharge process as the nucleocapsid structure of internal structure.And the carbon-coating of outer layer enhances electric conductivity, simultaneously work as isolating the effect that silica flour directly contacts with electrolyte, the volumetric expansion of silica flour in charge and discharge process can also be played restriction effect, substantially improve silica flour as lithium ion battery negative material cycle performance in charge and discharge process and high rate performance, make silicon based composite material have circulation and the high rate performance of excellence.
A kind of preparation method of Silicon Based Anode Materials for Lithium-Ion Batteries, concrete preparation process is as follows:
(1) prepare the compound water solution of the nickel that mole solubility is 0.1～3mol/L, then weigh a certain amount of silica flour and add solution, be stirred continuously and obtain mixed solution；
(2) adding alkaline solution in mixed solution, nickel produces precipitation, obtains Ni (OH)2It is attached to the mixed solution of silicon powder surface；
(3) step 2 prepared contains the mixed solution centrifugation of precipitation, drying, obtains Si/Ni (OH)2Pressed powder；
(4) by Si/Ni (OH)2Pressed powder joins in the ethanol solution of organic resin and stirs 1～2 hour, is then stirred continuously at 50～70 DEG C to being evaporated and obtains pressed powder；
(5) by above-mentioned pressed powder in a nitrogen atmosphere, with the heating rate of 5～20 DEG C/min, it is heated to 800-950 DEG C, and is incubated 1～4h, be then cooled to room temperature；
(6) material obtained in step 5 pulverized and sieve, obtaining the particle diameter D50 powder body between 5～30 μm, the i.e. present invention and there is (Si/Ni) C composite of nucleocapsid structure.
Wherein, in step (1), the mol ratio of silicon and nickel is n(Si): n(Ni)=100:(1～5), the particle diameter≤30nm of silica flour, the compound of nickel is one or more mixing in Nickel dichloride., nickel sulfate, nickel nitrate.
Wherein, the alkaline solution in step (2) is the one in sodium hydroxide, potassium hydroxide, ammonia, and solubility is 0.1～1mol/L, and the amount of addition is n(OH-): n(Ni)=(2～2.2): 1.
Wherein, the drying temperature in step (3) is 40～60 DEG C, and the time is 12～24 hours.
Wherein, in step (4) organic resin be in epoxy resin, phenolic resin or furfural resin one or more, the weight ratio of resin and silica flour is m(resin): m(Si)=(5～10): 100.
Use this technical scheme, utilize the carbon formed in organic resin pyrolytic process, use carbothermic method, by controlling the temperature and time of thermal reduction, the shell making nucleocapsid structure is made up of alloying with silicon compound and metal simple-substance, carbon source be pyrolysis after formed amorphous carbon layer cladding polymer.
Compared with prior art, the invention have the benefit that
First, use technical scheme, with silica flour as core, silicon forms the shell of composite with the alloy cpd of metallic nickel and the mixture of nickel, composition nucleocapsid structure within Silicon Based Anode Materials for Lithium-Ion Batteries, outer surface is carbon-coating cladding, improves silica flour as lithium ion battery negative material cycle performance in charge and discharge process and high rate performance, makes silicon based composite material have circulation and the high rate performance of excellence；
Second, use technical scheme, preparation (Si/Ni) C alloy composite material, outside the alloy cpd that in composite, Si Yu Ni is formed, some elemental nickel exists, and composite be nucleocapsid structure and with silica flour as core, silicon collectively constitute shell with alloy cpd and the nickel of metallic nickel.Silicon effectively raises high rate performance with the alloy cpd of metallic nickel and the introducing of nickel, and nucleocapsid structure effectively inhibits the volumetric expansion in silica flour charge and discharge process.Simultaneously, form at (Si/Ni) C alloy composite material surface carbon coating layer is the agraphitic carbon of pyrolysis, on the one hand silica flour is directly contacted with electrolyte the effect playing isolation, being prevented effectively from the formation of silicon powder surface instability SEI film, on the other hand the carbon-coating on surface adds the effect that the volumetric expansion of silica flour in charge and discharge process is also functioned to limit by the electric conductivity of composite simultaneously.
Accompanying drawing explanation
Fig. 1 is the cycle performance figure of the embodiment of the present invention 1.
Fig. 2 is the gram volume conservation rate figure of the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with specific embodiment, the preferably embodiment of the present invention is described in further detail.
Embodiment 1
A kind of preparation method of Silicon Based Anode Materials for Lithium-Ion Batteries, its preparation process is as follows:
(1) weighing Nickel dichloride. 2g, preparation solubility is the nickel chloride aqueous solution of 0.5mol/L, according to n(Si): the ratio of n(Ni)=100:5, add the silica flour of 8.64g, be stirred continuously and obtain mixed solution；
(2) in above-mentioned mixed solution, it is slowly added to the ammonia spirit of 0.5mol/L, altogether 61.7ml, generates precipitation, obtain Ni (OH)2It is attached to the mixed solution of silicon powder surface；
(3) step 2 prepared contains the mixed solution centrifugation of precipitation, drying, obtains Si/Ni (OH)2Pressed powder；
(4) weigh 0.86g phenolic resin and be dissolved in dehydrated alcohol, at the pressed powder added in step 3, after stirring 1～2 hour, be then stirred continuously at 50～70 DEG C to being evaporated and obtain pressed powder；
(5) by above-mentioned pressed powder in a nitrogen atmosphere, with the heating rate of 5 DEG C/min, it is heated to 900 DEG C, and is incubated 4h, be then cooled to room temperature；
(6) material obtained in step 5 pulverized and sieve, obtaining the particle diameter D50 powder body between 5～30 μm, the i.e. present invention and there is (Si/Ni) C composite of nucleocapsid structure.
With obtained (Si/Ni) C composite, PVDF, the mass ratio of conductive carbon black is that 85:10:5 is coated in Copper Foil as negative pole, and using metal lithium sheet as to electrode, the hexafluoro phosphorus lithium of 1mol/L, as electrolyte, is assembled into button cell.Button cell under the electric current density of 200mA/g, the cycle performance figure of this electrode material as it is shown in figure 1, capability retention as shown in Figure 2.Can be seen that the discharge capacity first of this composite reaches 825mAh/g, the capacity after 100 circulations still has 660mAh/g, and conservation rate is 80%.
Embodiment 2
A kind of preparation method of Silicon Based Anode Materials for Lithium-Ion Batteries, its preparation process is as follows:
(1) NiSO is weighed4·6H2O compound 10g, preparation solubility is the nickel chloride aqueous solution of 0.5mol/L, according to n(Si): the ratio of n(Ni)=100:7, add the silica flour of 14.87g, be stirred continuously and obtain mixed solution；
(2) in above-mentioned mixed solution, it is slowly added to the sodium hydroxide solution of 1mol/L, altogether 78ml, generates precipitation, obtain Ni (OH)2It is attached to the mixed solution of silicon powder surface；
(3) step 2 prepared contains the mixed solution centrifugation of precipitation, drying, obtains Si/Ni (OH)2Pressed powder；
(4) weigh 1.3g epoxy resin and be dissolved in dehydrated alcohol, at the pressed powder added in step 3, after stirring 1～2 hour, be then stirred continuously at 50～70 DEG C to being evaporated and obtain pressed powder；
(5) by above-mentioned pressed powder in a nitrogen atmosphere, with the heating rate of 10 DEG C/min, it is heated to 950 DEG C, and is incubated 3h, be then cooled to room temperature；
(6) material obtained in step 5 pulverized and sieve, obtaining the particle diameter D50 powder body between 5～30 μm, the i.e. present invention and there is (Si/Ni) C composite of nucleocapsid structure.
With obtained (Si/Ni) C composite, PVDF, the mass ratio of conductive carbon black is that 85:10:5 is coated in Copper Foil as negative pole, and using metal lithium sheet as to electrode, the hexafluoro phosphorus lithium of 1mol/L, as electrolyte, is assembled into button cell.Button cell is under the electric current density of 200mA/g, and the discharge capacity first of this electrode material reaches 990mAh/g, and the capacity after 100 circulations still has 772mAh/g, and conservation rate is 78%.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.Skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; the principle that the present invention is simply described described in above-described embodiment and description; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements both fall within scope of the claimed invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.

Claims (5)

1. a preparation method for Silicon Based Anode Materials for Lithium-Ion Batteries, its feature comprises the following steps:
(1) prepare the compound water solution of the nickel that mole solubility is 0.1～3mol/L, then weigh a certain amount of silica flour and add solution, be stirred continuously and obtain mixed solution；
(2) adding alkaline solution in mixed solution, nickel produces precipitation, obtains Ni (OH)2It is attached to the mixed solution of silicon powder surface；
(3) step 2 prepared contains the mixed solution centrifugation of precipitation, drying, obtains Si/Ni (OH)2Pressed powder；
(4) by Si/Ni (OH)2Pressed powder joins in the ethanol solution of organic resin and stirs 1～2 hour, is then stirred continuously at 50～70 DEG C to being evaporated and obtains pressed powder；
(5) by above-mentioned pressed powder in a nitrogen atmosphere, with the heating rate of 5～20 DEG C/min, it is heated to 800-950 DEG C, and is incubated 1～4h, be then cooled to room temperature；
(6) material obtained in step 5 pulverized and sieve, obtaining the particle diameter D50 powder body between 5～30 μm, the i.e. present invention and there is (Si/Ni) C composite of nucleocapsid structure.
2. according to the preparation method of a kind of Silicon Based Anode Materials for Lithium-Ion Batteries described in claim 1, it is characterized in that: in step (1), the mol ratio of silicon and nickel is n(Si): n(Ni)=100:(1～5), particle diameter≤the 30nm of silica flour, the compound of nickel is one or more mixing in Nickel dichloride., nickel sulfate, nickel nitrate.
3. according to the preparation method of a kind of Silicon Based Anode Materials for Lithium-Ion Batteries described in claim 1, it is characterized in that: the alkaline solution in step (2) is the one in sodium hydroxide, potassium hydroxide, ammonia, solubility is 0.1～1mol/L, and the amount of addition is n(OH-): n(Ni)=(2～2.2): 1.
4. according to the preparation method of a kind of Silicon Based Anode Materials for Lithium-Ion Batteries described in claim 1, it is characterized in that: the drying temperature in step (3) is 40～60 DEG C, the time is 12～24 hours.
5. according to the preparation method of a kind of Silicon Based Anode Materials for Lithium-Ion Batteries described in claim 1, it is characterized in that: in step (4) organic resin be in epoxy resin, phenolic resin or furfural resin one or more, the weight ratio of resin and silica flour is m(resin): m(Si)=(5～10): 100.
CN201610385411.6A 2016-06-03 2016-06-03 Preparation method of silicon-based negative electrode material for lithium ion battery Withdrawn CN105870423A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109037638A (en) * 2018-08-03 2018-12-18 东莞市迈科新能源有限公司 Carbon silicon core-shell material
CN110797517A (en) * 2019-10-23 2020-02-14 合肥国轩高科动力能源有限公司 Preparation method of nickel-silver alloy particle doped silicon-carbon negative electrode material
CN111326703A (en) * 2018-12-13 2020-06-23 丰田自动车株式会社 Nonaqueous electrolyte secondary battery
WO2022062321A1 (en) * 2020-09-27 2022-03-31 溧阳天目先导电池材料科技有限公司 Silicon-based negative electrode composite material and lithium secondary battery
CN117199327A (en) * 2023-11-07 2023-12-08 南通大学 Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109037638A (en) * 2018-08-03 2018-12-18 东莞市迈科新能源有限公司 Carbon silicon core-shell material
CN111326703A (en) * 2018-12-13 2020-06-23 丰田自动车株式会社 Nonaqueous electrolyte secondary battery
CN111326703B (en) * 2018-12-13 2023-04-18 丰田自动车株式会社 Nonaqueous electrolyte secondary battery
CN110797517A (en) * 2019-10-23 2020-02-14 合肥国轩高科动力能源有限公司 Preparation method of nickel-silver alloy particle doped silicon-carbon negative electrode material
WO2022062321A1 (en) * 2020-09-27 2022-03-31 溧阳天目先导电池材料科技有限公司 Silicon-based negative electrode composite material and lithium secondary battery
CN117199327A (en) * 2023-11-07 2023-12-08 南通大学 Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof
CN117199327B (en) * 2023-11-07 2024-05-03 南通大学 Quick-charging silicon-based negative electrode material for lithium battery and preparation method thereof

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Application publication date: 20160817