CN106099073A - The preparation method of composite cathode material for lithium ion cell, composite cathode material for lithium ion cell and lithium ion battery - Google Patents
The preparation method of composite cathode material for lithium ion cell, composite cathode material for lithium ion cell and lithium ion battery Download PDFInfo
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- 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
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to the preparation method of a kind of composite cathode material for lithium ion cell, composite cathode material for lithium ion cell and lithium ion battery, belong to lithium ion battery material technical field.The preparation method of this composite cathode material for lithium ion cell comprises the steps: to disperse silicon materials, polyacrylonitrile in spin solvent, prepares sandwich layer spinning liquid, is disperseed by polymethyl methacrylate in spin solvent, prepares shell layer spinning solution；Make fiber by coaxial electrostatic spinning technology, obtain being coated with presoma；Cladding presoma is added mixing in film for additive solution, adds heat extraction solvent, prepare into film precursor；One-tenth film precursor is sintered at 500 800 DEG C 1 24h and carries out carbonization treatment, to obtain final product.The composite negative pole material that the method for the present invention is prepared has the advantages such as gram volume is high, imbibition liquid-keeping property is strong, cycle performance is excellent, low temperature discharge ability is strong, is very suitable for the application in the field such as electric automobile, energy storage.
Description
Technical field
The present invention relates to the preparation method of a kind of composite cathode material for lithium ion cell, composite cathode material for lithium ion cell
And lithium ion battery, belong to technical field of lithium ion.
Background technology
The running voltage of lithium ion battery is high, have extended cycle life, energy density is big, and environmentally safe, portable
The fields such as formula electronic equipment, electric motor car, energy storage, communication are all widely used, along with lithium ion battery range of application not
Disconnected expansion, the requirement to the chemical property of lithium ion battery is more and more higher.
The performance of negative material has important impact to the chemical property of lithium ion battery, applies more lithium at present
Ion battery cathode material is graphite, and the good conductivity of graphite material, degree of crystallinity are high, but also have cheap, safety
High, makes graphite material occupy overwhelming majority application share in lithium ion battery negative material application.But, stone
The capacity of ink material is relatively low, the highest only 372mAh/g of theoretical capacity, significantly limit carrying further of battery whole volume
Rise.The theoretical capacity of silicium cathode material is more than 10 times of graphite, and about 4200mAh/g, the application of silicium cathode can be significantly
Improve the energy density of lithium ion battery.But, silicium cathode material in charge and discharge process, change in volume clearly, volume
Amplification, about 300%, causes electrode material efflorescence and inactivation, makes electrode structure change, and causes capacity attenuation very fast, shadow
Ring the cycle performance of battery.In order to overcome the disadvantages mentioned above of silicium cathode material, in prior art, general employing is mixed in silicon materials
The method of miscellaneous carbon coated weakens the change in volume impact in charge and discharge process of the silicium cathode material.
Application publication number is that the Chinese invention patent (Shen Qing Publication day be 2015 on December 2) of CN105118974 A is public
Open a kind of silicon based anode material and preparation method thereof, introduced carbon nano-fiber and reduce the volumetric expansion of nano silicon particles, keep away
Exempt from the phenomenon that silicon grain is broken, improve the mechanical strength of negative material.
Application publication number is that the Chinese invention patent (Shen Qing Publication day is on January 30th, 2013) of CN102903896A is open
A kind of silicon-carbon composite cathode material for lithium ion battery and preparation method thereof, this negative material is nucleocapsid structure, including
Nucleome and be coated on intermediate layer and the outermost layer of nucleome successively, nucleome is nano-silicon, and intermediate layer is amorphous carbon, and outermost layer is one
Dimension nano-carbon material, this negative material in the preparation, uses and silicon nanoparticle and organic carbon source is disperseed in organic solvent, dry
Microwave heating 2-180 minute under the conditions of inert atmosphere and temperature are 300-600 again after dry, cooling obtains amorphous carbon-coated nano
Silicon grain, is then coated with amorphous carbon silicon nanoparticle and nano-carbon material is scattered in organic solvent, 100-400 DEG C of temperature
Spray under degree cracking, obtain the silicon-carbon composite cathode material for lithium ion battery.This material can obtain being coated with at silicon face
The volumetric expansion of silicon materials can be provided buffering to make by the composite of the carbon-coating that two-layer is different, intermediate layer and outermost carbon-coating
With, significantly reduce the penalty of the negative material caused due to silicon volumetric expansion.
But, above-mentioned material is when discharge and recharge, and the cycle performance of material is the most poor, and its reason is probably carbon coating layer
Surface is not easily formed stable SEI film.It addition, preparation method process complexity, the poor stability of above two material, be difficult to industry
Metaplasia is produced.
Summary of the invention
It is an object of the invention to provide the preparation side of the good composite cathode material for lithium ion cell of a kind of cycle performance
Method.The prepared composite cathode material for lithium ion cell of offer said method is provided and uses this Compound Negative
The lithium ion battery of pole material.
For achieving the above object, the technical scheme of the preparation method of the composite cathode material for lithium ion cell of the present invention is:
The preparation method of a kind of composite cathode material for lithium ion cell, comprises the steps:
1) silicon materials, polyacrylonitrile are disperseed in spin solvent, prepare sandwich layer spinning liquid, by polymethyl methacrylate
Spin solvent disperses, prepares shell layer spinning solution；By coaxial electrostatic spinning technology by sandwich layer spinning liquid and shell layer spinning solution
Make fiber, obtain being coated with presoma；Described silicon materials, polyacrylonitrile, the mass ratio of polymethyl methacrylate are 1-3:5-
10:3-6；
2) film for additive is dissolved in film forming solvent make film for additive solution, by step 1) prepare cladding before
Drive body and add mixing in film for additive solution, add heat extraction film forming solvent, prepare into film precursor；Described cladding presoma with
The mass ratio of film for additive is 30-50:2-10；
3) one-tenth film precursor is sintered at 500-800 DEG C 1-24h and carry out carbonization treatment, to obtain final product.
Described film for additive is the one or two kinds of in lithium carbonate, sodium fluoride.
The concentration of described film for additive solution is the film for additive Han 2-5g in 100mL film forming solution.
Step 1) described silicon materials are porous silicon, the preparation method of this porous silicon includes: by kieselguhr with magnesium powder in non-oxygen
Under the property changed gas shield, it is incubated 6-12h, pickling after being warming up to 500-800 DEG C, to obtain final product；Described kieselguhr and the mass ratio of magnesium powder
For 5-10:5-10.
Described non-oxidizing gas main purpose is to provide non-oxidizing environment for kieselguhr sintering process, it is possible to use
Non-oxidizing gas of the prior art.In order to magnesium powder is aoxidized by the oxygen in kieselguhr, the non-oxidizing gas of the present invention is
Argon and the mixed gas of hydrogen.Described argon is 1:1 with the volume ratio of hydrogen.
The speed of described intensification is 1～5 DEG C/min.Described pickling uses hydrochloric acid.The concentration of described hydrochloric acid is 5-20%.Acid
The time washed is 10-60min.
Step 2) in cladding presoma is added in film for additive solution and is mixed by sonic oscillation 30min.
Step 2) enter under vacuum is for-0.05～-0.1MPa after in cladding presoma addition film for additive solution
Row vacuum impregnation.The described vacuum-impregnated time is 10-60min.
Described spin solvent is dimethylformamide.The volume of the dimethylformamide mixed with polyacrylonitrile is 100mL.
The volume of the dimethylformamide mixed with polymethyl methacrylate is 100mL.
Described film forming solvent is oxolane.
SiO in described kieselguhr2Content is not less than 80%.
The technical scheme of the composite cathode material for lithium ion cell of the present invention is:
A kind of composite cathode material for lithium ion cell using said method to prepare.
The technical scheme of the lithium ion battery of the present invention is:
A kind of lithium ion battery using above-mentioned composite cathode material for lithium ion cell.
The invention has the beneficial effects as follows:
The composite cathode material for lithium ion cell intensification preparation method of the present invention uses immersion-carbonization treatment technique, at silicon
Material surface forms carbon coating layer, substantially increases the specific surface area of silicon carbon material, improves the charge-discharge performance of material.This
Bright also utilization adds film for additive in tetrahydrofuran solvent, form a kind of thin film on cladding carbon-coating surface, improve following of material
The ring life-span, cycle life the most at low temperatures.
The composite negative pole material that the method for the present invention is prepared has that gram volume is high, imbibition liquid-keeping property strong, cycle performance
The advantages such as excellent, low temperature discharge ability is strong, the application being very suitable for the field such as electric automobile, energy storage uses this material to prepare
Lithium ion battery has preferable cycle life and cryogenic property.
Use electrostatic spinning technique can prepare homogeneous, stable, the filamentary structure of morphology controllable, be conducive to improving and bear
The structural homogeneity of pole material；Simultaneously can by adjust the concentration of electrostatic spinning liquid and receive plate distance, voltage can be made
Standby go out various parameters fibrous covering material, to meet the demand of different field.
Further, the preparation process of the porous silicon that the present invention uses relies on the catalysis characteristics of magnesium, accelerates material
Preparation process.
Further, clad is evenly coated at porous silicon surface by preparation process and forms the material knot of two-coat
Structure, is reducing during silicon uses while expansion rate and can improve the electrical conductivity of material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the composite negative pole material that embodiment 1 prepares.
Detailed description of the invention
Below in conjunction with the accompanying drawings embodiments of the present invention are described further.
Embodiment 1
The preparation method of the composite cathode material for lithium ion cell of the present embodiment comprises the steps:
1) by 8g SiO2Content be 95% kieselguhr mix with 8g magnesium powder, load in airtight quartz ampoule, be passed through Ar with
H2Volume ratio is the mixed gas of 1:1, is warming up to 650 DEG C with the programming rate of 3 DEG C/min, reacts 10h, the product that reaction obtains
With the chlorohydric acid pickling 30min that mass fraction is 10%, obtain porous silica material；
2) by 2g step 1) porous silica material of gained, 10g polyacrylonitrile (PAN) add 100mL dimethylformamide
(DMF) in, mix homogeneously, prepare sandwich layer spinning liquid；5g polymethyl methacrylate is dissolved in the dimethylformamide of 100mL
In, prepare shell layer spinning solution；By coaxial electrostatic spinning technology, sandwich layer spinning liquid and shell layer spinning solution are made silicon-polypropylene
Nitrile/polymethyl methacrylate nano fiber, obtains being coated with presoma through the pulverizing of omnipotent disintegrating machine, classification；
3) 40g is coated with persursor material and adds in there-necked flask, add the film for additive solution of 150mL, be evacuated to-
0.05MPa, sonic oscillation 30min, take out sample, after being heated to 80 DEG C of removing solvents at ambient pressure, is transferred in tube furnace,
At 750 DEG C, react 12h carry out carbonization treatment, prepare composite cathode material for lithium ion cell；Film for additive solution is by 2g's
Lithium carbonate adds prepared 150mL film for additive solution in oxolane.
Embodiment 2
The preparation method of the composite cathode material for lithium ion cell of the present embodiment comprises the steps:
1) by 5g SiO2Content be 80% kieselguhr mix with 10g magnesium powder, load in airtight quartz ampoule, be passed through Ar
With H2Volume ratio is the mixed gas of 1:1, is warming up to 500 DEG C with the programming rate of 1 DEG C/min, reacts 12h, the product that reaction obtains
Thing mass fraction is the chlorohydric acid pickling 60min of 5%, obtains porous silica material；
2) by 1g step 1) porous silica material of gained, 5g polyacrylonitrile (PAN) add 100mL dimethylformamide
(DMF) in, mix homogeneously, prepare sandwich layer spinning liquid；3g polymethyl methacrylate is dissolved in the dimethylformamide of 100mL
In, prepare shell layer spinning solution；By coaxial electrostatic spinning technology, sandwich layer spinning liquid and shell layer spinning solution are made silicon-polypropylene
Nitrile/polymethyl methacrylate nano fiber, obtains being coated with presoma through the pulverizing of omnipotent disintegrating machine, classification；
3) 30g is coated with persursor material and adds in there-necked flask, add the film for additive solution of 100mL, be evacuated to-
0.08MPa, sonic oscillation 30min, take out sample, after being heated to 80 DEG C of removing solvents at ambient pressure, is transferred in tube furnace,
At 500 DEG C, react 24h carry out carbonization treatment, prepare composite cathode material for lithium ion cell；Film for additive solution is by 5g's
Sodium fluoride adds prepared 100mL film for additive solution in oxolane.
Embodiment 3
The preparation method of the composite cathode material for lithium ion cell of the present embodiment comprises the steps:
1) by 10g SiO2Content be 99% kieselguhr mix with 5g magnesium powder, load in airtight quartz ampoule, be passed through Ar
With H2Volume ratio is the mixed gas of 1:1, is warming up to 800 DEG C with the programming rate of 5 DEG C/min, reacts 6h, the product that reaction obtains
Thing mass fraction is the chlorohydric acid pickling 10min of 20%, obtains porous silica material；
2) by 3g step 1) porous silica material of gained, 5g polyacrylonitrile (PAN) add 100mL dimethylformamide
(DMF) in, mix homogeneously, prepare sandwich layer spinning liquid；6g polymethyl methacrylate is dissolved in the dimethylformamide of 100mL
In, prepare shell layer spinning solution；By coaxial electrostatic spinning technology, sandwich layer spinning liquid and shell layer spinning solution are made silicon-polypropylene
Nitrile/polymethyl methacrylate nano fiber, obtains being coated with presoma through the pulverizing of omnipotent disintegrating machine, classification；
3) 50g is coated with persursor material and adds in there-necked flask, add the film for additive solution of 200mL, be evacuated to-
0.09MPa, sonic oscillation 30min, take out sample, after being heated to 80 DEG C of removing solvents at ambient pressure, is transferred in tube furnace,
At 800 DEG C, react 12h carry out carbonization treatment, prepare composite cathode material for lithium ion cell；Film for additive solution is by 3g's
Lithium carbonate adds prepared 200mL film for additive solution in oxolane.
Test example
The silicon-carbon cathode material (Shenzhen Bei Terui Science and Technology Ltd., model: Si/C) buied with market is as a comparison case.
1) physical and chemical performance test
The negative material of embodiment 1-3 and comparative example is carried out material particle size, specific surface area test, and testing standard is according to state
Method of testing in family's standard GB/T24533-2009 " silicon/carbon/graphite in lithium ion batteries class negative material " is carried out.Test result such as table 1
Shown in.
Composite negative pole material in embodiment 1 is scanned Electronic Speculum test, and test scanning electron microscope model used is Hitachi
S4800, test result is as shown in Figure 1.
2) charge-discharge property test
The negative material in embodiment 1-3 and comparative example is utilized to prepare button cell in accordance with the following steps: its preparation method
For: the negative material in the lithium ion battery negative material prepared in Example 1-3 respectively and comparative example, adds bonding respectively
Agent, conductive agent and solvent, be stirred slurrying, is coated on Copper Foil, through drying, rolling prepared negative plate；Binding agent used
For LA132 binding agent, conductive agent is SP, and solvent is redistilled water, negative material used, conductive agent SP, binding agent LA132
And the quality of redistilled water or volume are respectively 95g, 1g, 4g, 220mL；Use LiPF6/ EC+EMC+DMC (1:1:1) makees
For electrolyte, metal lithium sheet is to electrode, and barrier film uses polyethylene (PE), polypropylene (PP) or poly-second propylene (PEP) composite membrane,
Battery is assemblied in the glove box of applying argon gas and carries out.
Chemical property is carried out on the indigo plant electricity CT2001A type cell tester of Wuhan, and charging/discharging voltage scope is 0.005V
To 2.0V, charge-discharge magnification is 0.1C；Test first charge-discharge capacity and the efficiency first of each button cell respectively.
Test result is as shown in table 1.
The performance comparison of the negative material in table 1 embodiment 1-3 and comparative example
As can be seen from Table 1, the negative material of embodiment 1-3 is compared with the negative material of comparative example, and granularity is less, compares table
Area is relatively big, and discharge capacity has also increased than the negative material of comparative example first, adds the use of additive, material in material
Efficiency first also significantly improve.
3) imbibition liquid-keeping property test
Using the negative material in embodiment 1-3 and comparative example as negative material, using LiFePO4 as positive electrode, adopt
Use LiPF6/ EC+DEC (volume ratio is 1:1) is electrolyte, and Celgard 2400 film is barrier film, prepares the soft-package battery of 5Ah
B1, B2, B3 and C1 and corresponding cathode pole piece thereof, and test the imbibition liquid-keeping property of negative plate.Test result is shown in Table 2.
The imbibition water retainability of the negative plate that the negative material in table 2 embodiment 1-3 and comparative example prepares
| Example | Rate of liquid aspiration (mL/min) | Protect liquid rate (24h electrolyte content/0h electrolyte content) |
| Embodiment 1 | 6.1 | 95.3% |
| Embodiment 2 | 5.6 | 94.2% |
| Embodiment 3 | 4.8 | 94.4% |
| Comparative example | 2.1 | 83.7% |
As can be seen from Table 2, the imbibition liquid-keeping property of the negative material of embodiment 1-3 is significantly improved with comparative example,
Its reason is, material surface is coated with the material with carbon element that two-layer specific surface area is high, improves the imbibition liquid-keeping property of material.
Then utilize above-mentioned negative plate to make soft-package battery, test its cryogenic property and cycle performance, test result such as table 3
Shown in table 4.Wherein cryogenic property is charged with multiplying power 0.3C at 25 DEG C, the most respectively 25 DEG C, 0 DEG C ,-20 DEG C, at-40 DEG C
Test with 1.0C multiplying power discharging
The low temperature performance of the battery in table 3 embodiment 1-3 and comparative example
Note: the discharge capacity at a temperature of " conservation rate " refers to this in table 3 and the ratio of the discharge capacity at 25 DEG C.
As can be seen from Table 3, the cryogenic property of the soft-package battery that embodiment 1-3 is prepared is substantially better than comparative example, and it is former
Because of may be negative material in preparation process, add film formation at low temp agent lithium carbonate or sodium fluoride, improve under cryogenic
The transfer rate of lithium ion.
The charge-discharge performance of the soft-package battery that the negative material in table 4 embodiment 1-3 and comparative example prepares
| Initial capacity (mAh) | Capacity (mAh) after 500 times | Capability retention (%) | |
| Embodiment 1 | 5.2 | 4.6 | 88.7 |
| Embodiment 2 | 5.3 | 4.7 | 87.9 |
| Embodiment 3 | 5.1 | 4.5 | 87.3 |
| Comparative example | 5.2 | 4.3 | 82.5 |
As can be seen from Table 4, the cyclicity of that use embodiment 1-3 and prepared by the negative material of comparative example soft-package battery
Can compare, the cycle performance of the battery of embodiment is slightly better than comparative example, and its reason may be: porous silicon can in charge and discharge process
To slow down the expansion rate of material, simultaneously porous silicon formed nanometer, micron hole again can be with Electolyte-absorptive for material circulation mistake
Journey provides sufficient electrolyte；It addition, there is abundant duct in the silicon of nucleocapsid structure/carbon composite material, this some holes is tied
The existence of structure adds contacting of silicon grain and electrolyte, accelerates the transmission of lithium ion, improves the electrical conductivity of composite,
Therefore porous silicon carbon composite has more preferable chemical property.
Claims (9)
1. the preparation method of a composite cathode material for lithium ion cell, it is characterised in that comprise the steps:
1) silicon materials, polyacrylonitrile are disperseed in spin solvent, prepare sandwich layer spinning liquid, polymethyl methacrylate is being spun
Silk solvent disperses, prepares shell layer spinning solution；By coaxial electrostatic spinning technology, sandwich layer spinning liquid and shell layer spinning solution are made
Fiber, obtains being coated with presoma；Described silicon materials, polyacrylonitrile, the mass ratio of polymethyl methacrylate are 1-3:5-10:3-
6；
2) film for additive is dissolved in film forming solvent make film for additive solution, by step 1) prepare cladding presoma
Add in film for additive solution and mix, add heat extraction film forming solvent, prepare into film precursor；Described cladding presoma and film forming
The mass ratio of additive is 30-50:2-10；
3) one-tenth film precursor is sintered at 500-800 DEG C 1-24h and carry out carbonization treatment, to obtain final product.
The preparation method of composite cathode material for lithium ion cell the most according to claim 1, it is characterised in that: described film forming
Additive is the one or two kinds of in lithium carbonate, sodium fluoride.
The preparation method of composite cathode material for lithium ion cell the most according to claim 1, it is characterised in that: step 1) institute
Stating silicon materials is porous silicon, and the preparation method of this porous silicon includes: by kieselguhr and magnesium powder under non-oxidizing gas is protected, and rises
Temperature is incubated 6-12h, pickling after 500-800 DEG C, to obtain final product；Described kieselguhr is 5-10:5-10 with the mass ratio of magnesium powder.
The preparation method of composite cathode material for lithium ion cell the most according to claim 3, it is characterised in that: described non-oxygen
The property changed gas is the mixed gas of argon and hydrogen.
The preparation method of composite cathode material for lithium ion cell the most according to claim 1, it is characterised in that: step 2) will
Cladding presoma carries out vacuum impregnation after adding in film for additive solution under vacuum is for-0.05～-0.1MPa.
The preparation method of composite cathode material for lithium ion cell the most according to claim 1, it is characterised in that: described spinning
Solvent is dimethylformamide.
The preparation method of composite cathode material for lithium ion cell the most according to claim 1, it is characterised in that: described film forming
Solvent is oxolane.
8. the lithium-ion electric that the preparation method using composite cathode material for lithium ion cell as claimed in claim 1 prepares
Pond composite negative pole material.
9. the lithium ion battery using composite cathode material for lithium ion cell as claimed in claim 8.
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| CN113422009B (en) * | 2021-06-01 | 2022-03-18 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
| CN113422009A (en) * | 2021-06-01 | 2021-09-21 | 广东工业大学 | Lithium ion battery cathode material and preparation method and application thereof |
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