CN110518226A - A kind of silicon-carbon composite cathode material and preparation method thereof - Google Patents

A kind of silicon-carbon composite cathode material and preparation method thereof Download PDF

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CN110518226A
CN110518226A CN201910851737.7A CN201910851737A CN110518226A CN 110518226 A CN110518226 A CN 110518226A CN 201910851737 A CN201910851737 A CN 201910851737A CN 110518226 A CN110518226 A CN 110518226A
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silicon
composite cathode
cathode material
carbon composite
carbon
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CN110518226B (en
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许晓落
刘尚
安静
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Shanxi Shangtai lithium Technology Co.,Ltd.
Shijiazhuang Shangtai Technology Co., Ltd
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Shanxi Shangtai Lithium Technology Co Ltd
Shijiazhuang Shang Tai Technology Co Ltd
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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
    • 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
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/58—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
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention provides a kind of silicon-carbon composite cathode material, the negative electrode material is by coating lithium acetate on silicon-carbon complex material surface, wherein lithium acetate has the property similar with SEI film, so that it is reduced the consumption of lithium ion in charge and discharge process, improves the first charge discharge efficiency of its Si-C composite material；The characteristic that surface coating layer lithium acetate has lithium ion content high simultaneously makes it provide sufficient lithium ion in charge and discharge process, improves the multiplying power and cycle performance of its material.The kernel of silicon-carbon composite cathode material provided by the invention is reacted using silane coupling agent with silane compound, form cross-linked polymer, obtain stablizing the silicon oxide compound of reticular structure, and titania additive is wherein, by the high characteristic of the high conductivity of titanium dioxide and voltage platform, the electric conductivity and security performance of its material are improved；Conductive agent strong using large specific surface area and conductivity simultaneously, further increases the electric conductivity of its silicon carbon material.

Description

A kind of silicon-carbon composite cathode material and preparation method thereof
Technical field
The invention belongs to field of lithium ion battery material, and in particular to a kind of silicon-carbon composite cathode material and its preparation side Method.
Background technique
Increase with the marketization to high-energy-density density lithium ion battery requirements, market demands negative electrode of lithium ion battery material Material has high specific capacity and cycle performance, and it is raw material that negative electrode of lithium ion battery currently on the market, which mostly uses greatly graphite, However the theoretical capacity of graphite is only 372mAh/g, oneself is difficult to meet market to the higher requirement of cathode.Silicon materials Yin Qigao The advantages such as theoretical capacity, lower de- reason current potential and storage capacity abundant up to 4200mAh/g are unanimously paid attention to by researcher.But It is that silicon generates huge volume change in charge and discharge process, variation can achieve the 300% of original volume, keep silicon structure fast Speed is by dusting and destruction, relatively low its high rate performance of influence of the conductivity of material.Meanwhile electrolyte is contacted with silicon in silicon face shape At the SEI film of stability difference, efficiency for charge-discharge greatly reduces, thereby reduces cycle performance.
The defect of carbon silicon materials seriously affects the industrialization promotion of its silicon carbon material, although the nanometer that researcher passes through material Change, the means such as alloying and composite carbon-based material improve the volume change and conductivity problems of material, than if any researcher The problem of silicon materials electric conductivity difference is compensated by using alloy is formed with amorphous carbon and silicon materials.But silicium cathode is multi-party The problem of face, never obtains the problems such as system solution, especially first charge discharge efficiency relatively low problem.
Number of patent application are as follows: 201610807619.2 Chinese patent application is disclosed containing artificial SEI layers high volume specific volume The silicon-carbon cathode material of amount and cycle performance, it is amorphous carbon coating layer which, which is by a kind of secondary granulation, outer shell, interior Shell is fine and close LiF film, the meso-phase graphite structure composition that kernel is evenly dispersed nano-silicon, with improve material circulation and its First charge discharge efficiency.But the electric conductivity of material does not improve and its first charge discharge efficiency increase rate is unobvious, the reason for this is that the LiF of inner casing Film is inoranic membrane and general with the compatibility of organic electrolyte, can not reach good cycle performance.
Summary of the invention
For the technical problem more than solving, the present invention provides a kind of silicon-carbon composite cathode material, his Compound Negative of the silicon Pole material envelope contains the lithium acetate organic film of based solid electrolyte film (SEI) ingredient, and kernel contains the silicon oxidation of titanium dioxide Compound composite material, the high titanium dioxide of conductivity is adulterated by organic film with improve first charge discharge efficiency, the high rate performance of material with And cycle performance.
The object of the present invention is to provide a kind of silicon-carbon composite cathode materials.
It is a further object of the present invention to provide the preparation methods of above-mentioned silicon-carbon composite cathode material.
Silicon-carbon composite cathode material provided by the invention, the silicon-carbon composite cathode material are core-shell structure, inner nuclear material It include 67.5~82.5wt% of silicon oxide compound, 7.5~12.375wt% of conductive agent, titanium dioxide 7.5 according to weight percent ~12.375wt%, surplus are agraphitic carbon；Sheathing material includes 98~99wt% of lithium acetate according to weight percent, and surplus is Neopelex；The shell with a thickness of 50~500nm.
Silicon-carbon composite cathode material provided by the invention is core-shell structure, and wherein kernel includes silicon oxide compound, conductive agent, two Titanium oxide and agraphitic carbon, silicon oxide compound are reticular structure, titania additive wherein, by titanium dioxide conductivity by force and The high characteristic of voltage platform improves conductivity and security performance, while having agraphitic carbon in the Surface Creation of inner nuclear material, improves The electric conductivity of material reduces the Probability of side reaction.Sheathing material is the lithium acetate containing a small amount of neopelex, Lithium acetate has the property similar with solid electrolyte film, it is made to reduce the consumption of lithium ion in charge and discharge process, improves silicon The first charge discharge efficiency of O compoiste material improves the multiplying power and cycle performance of material, sodium dodecyl benzene sulfonate-doped in lithium acetate, Carry out sodium ion doping for material strips, promotes the structural stability of negative electrode material.
Preferably, the silicon oxide compound is SiOX, wherein 0.5≤X≤2.
Preferably, the conductive agent is one of carbon nanotube, vapor deposition carbon fiber, super carbon black and graphene.
The present invention provides the preparation method of above-mentioned silicon-carbon composite cathode material, comprising the following steps:
(1) silane compound, silane coupling agent are added in organic solvent, after mixing, add conductive agent, two Titanium oxide carries out ball milling, is carbonized under an argon atmosphere, obtains Si-C composite material；
(2) lithium acetate is dissolved in and is configured to the lithium acetate solution that concentration is 1~10% in solvent, dodecane is then added The Si-C composite material and distilled water that base benzene sulfonic acid sodium salt, step (1) obtain, preparing becomes uniform solution, and spray drying obtains The silicon-carbon composite cathode material.
The preparation method of silicon-carbon composite cathode material provided by the invention prepares inner nuclear material first, and inner nuclear material is with silane Compound, silane coupling agent, conductive agent, titanium dioxide and organic solvent are raw material, and silane compound and silane coupling agent exist Reaction is crosslinked in organic solvent, generates polysilane compound, the active group and silane compound in silane coupling agent Alkyl group, which reacts, generates cross-linking compounds, and boiling point can obviously be higher than the boiling of silane compound/silane coupling agent itself Point, the polysilane based compounds surface being formed simultaneously can adsorb a little organic solvents, then by carbonization, can there is solvent volatilization Situation also can deposit the ingredient of generation carbon on silane-based compound surface, may eventually form the change of the elements such as silicon, carbon, oxygen formation Close object.The hydrocarbon in organic solvent on the surface of the material is adsorbed during carbonization by being formed after high temperature without fixed Type carbon forms the surface of inner nuclear material, increases the conductivity of material.
Preferably, in step (1), the silane compound is bromotrimethylsilane, chlorotriethyl silane, dimethyl chloride Silane, a phenyl trichlorosilane, n-octyl trichlorosilane, dimethyldichlorosilane, diisopropyl chlorosilane and trimethyl silicane One of alkanisation diazomethane.
Preferably, in step (1), the silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-(2,3- epoxies Third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, octyltri-ethoxysilane and two One of methyl dimethoxysilane.
Preferably, the organic solvent is, N-Methyl pyrrolidone, carbon tetrachloride, benzene, dimethylbenzene, one in hexamethylene Kind.
Preferably, in step (1), the silane compound: silane coupling agent: conductive agent: titanium dioxide: organic solvent Weight ratio is 10~30: 1~5: 1~5: 1~5: 100~500.
Preferably, in step (1), the temperature of the carbonization is 780~820 DEG C, time 6h.
Preferably, in step (2), the solvent is the mixed solution of second alcohol and water, and the volume ratio of ethyl alcohol and water is 1: 1.
Preferably, in step (2), the lithium acetate, Si-C composite material, neopelex weight ratio be 1 ~3: 100: 0.5~2.
Preferably, the intake air temperature of spray drying described in step (2) be 120~180 DEG C, air outlet temperature be 80~ 120℃。
The invention has the benefit that
1. silicon-carbon composite cathode material provided by the invention by silicon-carbon complex material surface coat lithium acetate, wherein Lithium acetate has the property similar with SEI film, so that it is reduced the consumption of lithium ion in charge and discharge process, it is compound to improve its silicon-carbon The first charge discharge efficiency of material；The characteristic that surface coating layer lithium acetate has lithium ion content high simultaneously, makes it in charge and discharge process Sufficient lithium ion is provided, the multiplying power and cycle performance of its material are improved.
2. the kernel of silicon-carbon composite cathode material provided by the invention is occurred anti-using silane coupling agent and silane compound It answers, forms cross-linked polymer, the characteristic with stable structure, and titania additive is wherein, by titanium dioxide conduction The characteristic that rate is strong and voltage platform is high, improves the conductivity and security performance of its material；Large specific surface area and conduction are utilized simultaneously The strong conductive agent of rate, further increases the electric conductivity of its silicon carbon material.
3. preparation method provided by the invention by the carbonization of material under an inert atmosphere, makes it raw on inner nuclear material surface At amorphous carbon material, be conducive to the conductivity for increasing silicon, the bulk effect that buffering silicon generates during deintercalation improves it and leads Probability that is electrical and reducing its side reaction.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with It obtains other drawings based on these drawings.
Fig. 1 is the SEM figure for the silicon-carbon composite cathode material that embodiment 1 obtains.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work Other embodiment belongs to the range that the present invention is protected.
Embodiment 1
A kind of silicon-carbon composite cathode material, the negative electrode material are core-shell structure, and inner nuclear material is according to weight percent packet 74~75wt% of silicon oxide compound, 8.25~11.25wt% of conductive agent, 8.25~11.25wt% of titanium dioxide are included, surplus is nothing Sizing carbon；Sheathing material includes 98~99wt% of lithium acetate according to weight percent, and surplus is neopelex；It is described Shell with a thickness of 50~500nm.
The preparation method of above-mentioned silicon-carbon composite cathode material, comprising the following steps:
(1) 20g bromotrimethylsilane, 3g gamma-aminopropyl-triethoxy-silane are added to the N- methyl pyrrole of 300ml first In pyrrolidone organic solvent after mixing, then 3g carbon nanotube and 3g titanium dioxide are added, and carries out wet ball grinding, ball milling turns 500 revs/min, time 12h of speed, then 800 DEG C of carbonization 6h under an argon atmosphere, obtain Si-C composite material；
(2) 2g lithium acetate is dissolved in 40ml ethyl alcohol and water mixed solvent, the body of the in the mixed solvent second alcohol and water Product is configured to the lithium acetate solution that mass concentration is 5%, the silicon-carbon composite wood that 100g step (1) obtains then is added than being 1: 1 Material, 1g neopelex and 200ml secondary distilled water are configured to uniform solution, described spraying by spray drying Dry intake air temperature is set as 150 DEG C, and air outlet temperature is set as 100 DEG C, obtain shell be coated with lithium acetate silicon-carbon it is compound Negative electrode material.
Embodiment 2
A kind of silicon-carbon composite cathode material, the negative electrode material are core-shell structure, and inner nuclear material is according to weight percent packet 67.5~74.25wt% of silicon oxide compound, 7.5~8.25wt% of conductive agent, 7.5~8.25wt% of titanium dioxide are included, surplus is Agraphitic carbon；Sheathing material includes 98~99wt% of lithium acetate according to weight percent, and surplus is neopelex；Institute State shell with a thickness of 50~500nm.
The preparation method of above-mentioned silicon-carbon composite cathode material, comprising the following steps:
(1) 10g chlorotriethyl silane, 1g γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane are added to 100ml tetra- In chlorination carbon organic solvent after mixing, 1g vapor deposition carbon fiber and 1g titanium dioxide are added, and carries out wet ball grinding, The revolving speed of ball milling is 500 revs/min, time 12h, and then 780 DEG C of carbonization 6h under an argon atmosphere, obtain Si-C composite material；
(2) 1g lithium acetate is dissolved in 100ml ethyl alcohol and water mixed solvent, the body of the in the mixed solvent second alcohol and water Product is configured to the lithium acetate solution that mass concentration is 1%, the silicon-carbon composite wood that 100g step (1) obtains then is added than being 1: 1 Material, 0.5g neopelex and 200ml secondary distilled water are configured to uniform solution, are spray-dried, described spraying dry Dry intake air temperature is set as 120 DEG C, and air outlet temperature is set as 80 DEG C, obtains the silicon-carbon Compound Negative that shell is coated with lithium acetate Pole material.
Embodiment 3
A kind of silicon-carbon composite cathode material, the negative electrode material are core-shell structure, and inner nuclear material is according to weight percent packet 75~82.5wt% of silicon oxide compound, 11.25~12.375wt% of conductive agent, titanium dioxide 11.25~12.375wt% are included, it is remaining Amount is agraphitic carbon；Sheathing material includes 98~99wt% of lithium acetate according to weight percent, and surplus is dodecyl benzene sulfonic acid Sodium；The shell with a thickness of 50~500nm.
The preparation method of above-mentioned silicon-carbon composite cathode material, comprising the following steps:
(1) 30g dimethyldichlorosilane, 5g γ-(methacryloxypropyl) propyl trimethoxy silicane are added to 500ml In dimethylbenzene organic solvent after mixing, 5g graphene and 5g titanium dioxide are added, and carries out wet ball grinding, ball milling turns Speed is 500 revs/min, time 12h, and then 820 DEG C of carbonization 6h under an argon atmosphere, obtain Si-C composite material；
2) 3g lithium acetate is dissolved in 30ml ethyl alcohol and water mixed solvent, the volume of the in the mixed solvent second alcohol and water Than being 1: 1, it is configured to the lithium acetate solution that mass concentration is 10%, silicon-carbon composite wood obtained in 100g step (1) so is added Material, 2g neopelex and its 200ml secondary distilled water are configured to uniform solution, are spray-dried, the spray drying Intake air temperature is set as 180 DEG C, and air outlet temperature is set as 120 DEG C, obtains the silicon-carbon Compound Negative that shell is coated with lithium acetate Pole material.
Comparative example 1
A kind of silicon-carbon composite cathode material, the negative electrode material, which includes the following steps, to be prepared:
20g bromotrimethylsilane is added in the N-Methyl pyrrolidone organic solvent of 300ml after mixing first, The agent of 3g carbon nanotube conducting is added, and carries out wet ball grinding, the revolving speed of ball milling is 500 revs/min, time 12h, then in argon gas The lower 800 DEG C of carbonizations 6h of atmosphere, obtains Si-C composite material.
Test example
1.SEM test
SEM test is carried out to the silicon composite cathode material that embodiment 1 obtains, test results are shown in figure 1.As shown in Figure 1, Uniformly, rationally, grain diameter is between 5~15 μm for the material granule size distribution.
2. button cell is tested
It is assembled silicon composite cathode material obtained in Examples 1 to 3 and comparative example 1 as lithium ion battery negative material At button cell.
Specifically the preparation method comprises the following steps: adding binder, conductive agent and solvent in lithium ion battery negative material, it is stirred Slurrying is coated on copper foil, by drying, rolling obtained negative electrode tab；Binder used is LA132, and conductive agent is to conductive charcoal Black (SP), solvent are N-Methyl pyrrolidone (NMP), and negative electrode material, the usage ratio of SP, LA132, NMP are 95g: 1g: 4g: 220mL；LiPF in electrolyte6For electrolyte, the mixture of the EC and DEC of volume ratio 1: 1 are solvent；Metal lithium sheet is to electricity Pole, diaphragm use polypropylene (PP) film.Button cell is assemblied in the glove box of applying argon gas and carries out.Chemical property is in Wuhan indigo plant It is carried out on electric CT2001A type cell tester, charging/discharging voltage range is 0.005V~2.0V, charge-discharge velocity 0.1C.It surveys Test result is as shown in table 1.
The different negative electrode material the performance test results of table 1
The specific volume for the silicon-carbon composite cathode material that the embodiment of the present invention 1~3 is prepared it can be seen from the data in table 1 Amount and its first charge discharge efficiency are substantially better than comparative example 1.Outside the surface cladding lithium acetate of the inner nuclear material for the negative electrode material that this hair provides Shell improves the quantity of lithium ion in charge and discharge process, can provide sufficient lithium ion to form SEI film, and then improve it for the first time Efficiency and specific capacity.The structural stability of its material is improved by adding silane coupling agent simultaneously, and then improves its material gram appearance Amount plays.
3. soft-package battery is tested
Negative electrode tab is made using the Si-C composite material in Examples 1 to 3 and comparative example as negative electrode material, with ternary material (Li(Ni0.6Co0.2Mn0.2)O2) it is positive electrode；LiPF in electrolyte6For electrolyte, the ethylene carbonate of volume ratio 1: 1 (EC) and the mixture of diethyl carbonate (DEC) is solvent；Using 2400 film of Celgard as diaphragm, 5Ah soft-package battery is prepared, Labeled as C1, C2, C3 and D1.
3.1 imbibition abilities protect the test of liquid rate
3.1.1 imbibition ability
Using the buret of 1mL, and electrolyte VmL is drawn, a drop is added dropwise in pole piece, and carry out timing, until electricity Solution liquid absorption finishes, and record the time t, calculates the rate of liquid aspiration V/t of pole piece.Test result is as shown in table 2.
3.1.2 the test of liquid rate is protected
The theoretical liquid absorption amount m of pole piece is calculated according to pole piece parameter1, and weigh the weight m of pole piece2, pole piece is placed later Impregnated into electrolyte weigh for 24 hours pole piece weight be m3, calculate pole piece liquid absorption amount m3-m2, and calculate according to the following formula: protect liquid Rate=(m3-m2) * 100%/m1.Test result is as shown in table 2.
3.2 pole piece resistivity, rebound rate test
3.2.1 pole piece resistivity measurement
Using the resistivity of resistivity tester test pole piece, test result is as shown in table 3.
3.2.2 pole piece rebound rate is tested
It uses calibrator to test the average thickness of its pole piece as D1 first, pole piece is placed on to 80 DEG C of vacuum drying later Dry 48h in case, test pole piece with a thickness of D2, and be calculated as follows: rebound rate=(D2-D1) * 100%/D1.Test result As shown in table 3.
The test of 3.3 cycle performances
With charge-discharge magnification be 1C/1C, voltage range is 2.8V~4.2V, and following for battery is tested at 25 ± 3 DEG C of temperature Ring performance.Test result is as shown in table 4.
The imbibition liquid-keeping property test result of pole piece made from the different negative electrode materials of table 2
From table 2 it can be seen that the imbibition liquid-keeping property of silicon-carbon composite cathode material obtained by Examples 1 to 3 is apparently higher than pair Ratio 1.The experimental results showed that silicon-carbon composite cathode material imbibition liquid-keeping property with higher provided by the invention.This is main It is to have because containing organo-lithium compound in the shell clad of silicon-carbon composite cathode material provided by the invention with electrolyte Preferable compatibility can be improved the imbibition liquid-keeping property of its pole piece；And the silicon-carbon composite cathode material of Examples 1 to 3 has There is biggish specific surface area, further improves the imbibition liquid-keeping property of material.
The rebound rate test result of pole piece made from the different negative electrode materials of table 3
Group Pole piece rebound rate (%) Pole piece resistivity (m Ω)
Embodiment 1 12.7 16.8
Embodiment 2 13.6 17.9
Embodiment 3 15.5 20.1
Comparative example 1 19.6 178.5
It can be seen from the data in Table 3 that anti-using the negative electrode tab of the preparation of silicon-carbon composite cathode material obtained by Examples 1 to 3 Bullet rate is significantly lower than comparative example 1, i.e., has lower rebound using negative electrode tab made from silicon-carbon composite cathode material of the invention Rate.This is because the present invention makes its silane compound form reticular structure by adding silane coupling agent in the material, and at it After form silicon oxide compound, improve the structural stability of its material, and then reduce the rebound rate of pole piece, meanwhile, contain in material The high titanium dioxide of conductivity and conductive agent are conducive to improve the electronic conductivity of material, and then reduce the resistivity of pole piece.
The cycle performance of battery made from the different negative electrode materials of table 4
Battery Negative electrode material Recycle 500 capacity retention ratios (%)
C1 Embodiment 1 84.62
C2 Embodiment 2 83.78
C3 Embodiment 3 82.39
D1 Comparative example 1 75.76
As can be seen from Table 4, the cycle performance of battery made from silicon-carbon composite cathode material provided by the invention is obviously excellent In comparative example 1.This is because pole piece made from silicon-carbon composite cathode material provided by the invention has lower expansion rate, filling The structure of pole piece is more stable in discharge process, improves its cycle performance.In addition, silicon-carbon composite cathode material of the invention has There is the characteristic that lithium ion content is high, to provide sufficient lithium ion in charge and discharge process, further improves the cyclicity of battery Energy.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.

Claims (10)

1. a kind of silicon-carbon composite cathode material, which is characterized in that the silicon-carbon composite cathode material is core-shell structure, inner nuclear material It include 67.5~82.5wt% of silicon oxide compound, 7.5~12.375wt% of conductive agent, titanium dioxide 7.5 according to weight percent ~12.375wt%, surplus are agraphitic carbon；Sheathing material includes 98~99wt% of lithium acetate according to weight percent, and surplus is Neopelex；The shell with a thickness of 50~500nm.
2. silicon-carbon composite cathode material according to claim 1, which is characterized in that the silicon oxide compound is SiOX, In 0.5≤X≤2.
3. silicon-carbon composite cathode material according to claim 1, which is characterized in that the conductive agent is carbon nanotube, gas Mutually one of deposition carbon fiber, super carbon black and graphene.
4. the preparation method of silicon-carbon composite cathode material according to claim 1, which comprises the following steps:
(1) silane compound, silane coupling agent are added in organic solvent, after mixing, add conductive agent, titanium dioxide Titanium carries out ball milling, is carbonized under an argon atmosphere, obtains Si-C composite material；
(2) lithium acetate is dissolved in and is configured to the lithium acetate solution that concentration is 1~10% in solvent, detergent alkylate is then added The Si-C composite material and distilled water that sodium sulfonate, step (1) obtain, preparing becomes uniform solution, spray drying, obtains described Silicon-carbon composite cathode material.
5. the preparation method of silicon-carbon composite cathode material according to claim 4, which is characterized in that described in step (1) Silane compound be bromotrimethylsilane, chlorotriethyl silane, dimethylchlorosilane, a phenyl trichlorosilane, n-octyl three One of chlorosilane, dimethyldichlorosilane, diisopropyl chlorosilane and trimethyl silicone hydride diazomethane.
6. the preparation method of silicon-carbon composite cathode material according to claim 4, which is characterized in that described in step (1) Silane coupling agent be γ~aminopropyl triethoxysilane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, γ-(first One of base acryloyl-oxy) propyl trimethoxy silicane, octyltri-ethoxysilane and dimethyldimethoxysil,ne.
7. the preparation method of silicon-carbon composite cathode material according to claim 4, which is characterized in that described in step (1) Silane compound: silane coupling agent: conductive agent: titanium dioxide: the weight ratio of organic solvent be 10~30:1~5:1~5:1~ 5:100~500.
8. the preparation method of silicon-carbon composite cathode material according to claim 4, which is characterized in that described in step (1) The temperature of carbonization is 780~820 DEG C, time 6h.
9. the preparation method of silicon-carbon composite cathode material according to claim 4, which is characterized in that described in step (2) Solvent is the mixed solution of second alcohol and water, and the volume ratio of ethyl alcohol and water is 1:1.
10. the preparation method of silicon-carbon composite cathode material according to claim 4, which is characterized in that in step (2), institute State lithium acetate, Si-C composite material, neopelex weight ratio be 1~3:100:0.5~2.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111293299A (en) * 2020-02-28 2020-06-16 苏州清陶新能源科技有限公司 Modified metal lithium negative electrode battery and preparation method thereof
CN111326727A (en) * 2020-03-09 2020-06-23 洛阳联创锂能科技有限公司 Multi-component silicon-oxygen negative electrode material for lithium ion battery and preparation method thereof
CN112289987A (en) * 2020-09-30 2021-01-29 合肥国轩高科动力能源有限公司 Organic-inorganic composite silicon-based negative electrode material and preparation method and application thereof
CN113889593A (en) * 2020-07-02 2022-01-04 洛阳月星新能源科技有限公司 Preparation method of hard carbon-coated soft carbon composite material
CN114430029A (en) * 2021-12-13 2022-05-03 深圳先进技术研究院 Composite modified graphite material, positive electrode material of bi-ion battery, negative electrode material of bi-ion battery and bi-ion battery
CN114566619A (en) * 2021-12-25 2022-05-31 河南大森林生物科技有限公司 Green method for preparing lithium ion battery composite negative electrode material by adopting silicon-containing biomass
CN114843482A (en) * 2022-05-23 2022-08-02 常州烯源谷新材料科技有限公司 Core-shell silicon-carbon composite material and preparation method and application thereof
CN115020710A (en) * 2022-07-11 2022-09-06 陕西君和聚源科技有限公司 Low-expansion silicon-based composite negative electrode material, preparation method thereof and lithium ion battery
CN116230911A (en) * 2023-03-10 2023-06-06 内蒙古欣源石墨烯科技股份有限公司 High-power silicon-carbon negative electrode composite material and preparation method thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101811755A (en) * 2009-11-27 2010-08-25 北京工业大学 Method for preparing sodium dodecyl benzene sulfonate doped titanium catalyzed electrode
CN104091937A (en) * 2014-07-18 2014-10-08 深圳市振华新材料股份有限公司 Lithium titanate-coated surface-treated graphite negative electrode material, preparation method and application of negative electrode material
CN107623122A (en) * 2017-10-18 2018-01-23 张玉贞 A kind of preparation method of lithium battery spherical nucleocapsid lithium iron phosphate positive material
CN108054358A (en) * 2017-12-07 2018-05-18 湘潭大学 It is a kind of for composite negative pole material of lithium ion battery and preparation method thereof
CN108063232A (en) * 2017-12-15 2018-05-22 徐军红 A kind of silicon-carbon composite cathode material and preparation method thereof, lithium ion battery
WO2018099754A1 (en) * 2016-11-29 2018-06-07 Basf Se Process for making a coated oxide material, and vessel combination suitable for such process
CN108550827A (en) * 2018-05-08 2018-09-18 广东迈纳科技有限公司 A kind of preparation method of three-dimensional porous shape silicon-carbon cathode material and application
CN108987717A (en) * 2018-07-18 2018-12-11 开封大学 A kind of lithium ion battery silicon based composite material and preparation method thereof
CN109671943A (en) * 2018-12-26 2019-04-23 成都爱敏特新能源技术有限公司 A kind of Gao Shouxiao silicon-carbon composite cathode material and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101811755A (en) * 2009-11-27 2010-08-25 北京工业大学 Method for preparing sodium dodecyl benzene sulfonate doped titanium catalyzed electrode
CN104091937A (en) * 2014-07-18 2014-10-08 深圳市振华新材料股份有限公司 Lithium titanate-coated surface-treated graphite negative electrode material, preparation method and application of negative electrode material
WO2018099754A1 (en) * 2016-11-29 2018-06-07 Basf Se Process for making a coated oxide material, and vessel combination suitable for such process
CN107623122A (en) * 2017-10-18 2018-01-23 张玉贞 A kind of preparation method of lithium battery spherical nucleocapsid lithium iron phosphate positive material
CN108054358A (en) * 2017-12-07 2018-05-18 湘潭大学 It is a kind of for composite negative pole material of lithium ion battery and preparation method thereof
CN108063232A (en) * 2017-12-15 2018-05-22 徐军红 A kind of silicon-carbon composite cathode material and preparation method thereof, lithium ion battery
CN108550827A (en) * 2018-05-08 2018-09-18 广东迈纳科技有限公司 A kind of preparation method of three-dimensional porous shape silicon-carbon cathode material and application
CN108987717A (en) * 2018-07-18 2018-12-11 开封大学 A kind of lithium ion battery silicon based composite material and preparation method thereof
CN109671943A (en) * 2018-12-26 2019-04-23 成都爱敏特新能源技术有限公司 A kind of Gao Shouxiao silicon-carbon composite cathode material and preparation method thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111293299A (en) * 2020-02-28 2020-06-16 苏州清陶新能源科技有限公司 Modified metal lithium negative electrode battery and preparation method thereof
CN111293299B (en) * 2020-02-28 2021-07-27 苏州清陶新能源科技有限公司 Modified metal lithium negative electrode battery and preparation method thereof
CN111326727A (en) * 2020-03-09 2020-06-23 洛阳联创锂能科技有限公司 Multi-component silicon-oxygen negative electrode material for lithium ion battery and preparation method thereof
CN113889593A (en) * 2020-07-02 2022-01-04 洛阳月星新能源科技有限公司 Preparation method of hard carbon-coated soft carbon composite material
CN112289987A (en) * 2020-09-30 2021-01-29 合肥国轩高科动力能源有限公司 Organic-inorganic composite silicon-based negative electrode material and preparation method and application thereof
CN114430029A (en) * 2021-12-13 2022-05-03 深圳先进技术研究院 Composite modified graphite material, positive electrode material of bi-ion battery, negative electrode material of bi-ion battery and bi-ion battery
CN114566619A (en) * 2021-12-25 2022-05-31 河南大森林生物科技有限公司 Green method for preparing lithium ion battery composite negative electrode material by adopting silicon-containing biomass
CN114566619B (en) * 2021-12-25 2023-11-28 河南大森林生物科技有限公司 Green method for preparing lithium ion battery composite anode material by using siliceous biomass
CN114843482A (en) * 2022-05-23 2022-08-02 常州烯源谷新材料科技有限公司 Core-shell silicon-carbon composite material and preparation method and application thereof
CN115020710A (en) * 2022-07-11 2022-09-06 陕西君和聚源科技有限公司 Low-expansion silicon-based composite negative electrode material, preparation method thereof and lithium ion battery
CN116230911A (en) * 2023-03-10 2023-06-06 内蒙古欣源石墨烯科技股份有限公司 High-power silicon-carbon negative electrode composite material and preparation method thereof
CN116230911B (en) * 2023-03-10 2024-04-16 内蒙古欣源石墨烯科技股份有限公司 High-power silicon-carbon negative electrode composite material and preparation method thereof

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