CN104900910A - Lithium ion battery based on silicon cathode of carbon fiber cloth barrier layer - Google Patents
Lithium ion battery based on silicon cathode of carbon fiber cloth barrier layer Download PDFInfo
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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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- 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
Abstract
The invention relates to a lithium ion battery based on silicon cathode of a carbon fiber cloth barrier layer and belongs to the field of electrochemical batteries. The silicone cathode of the lithium ion battery comprises a current collector and active material coated with the current collector, the carbon fiber cloth barrier is added between the active material and a diaphragm, the active material comprises 60-80% of silicon powder, 30-10% of conductive agent and 30-10% of adhesive, and the carbon fiber cloth is 155-175 g/cm3 dense and 0.33-0.36 mm thick. The carbon fiber cloth is used as the barrier layer between the active material and the diaphragm, and capacity fading and short service life due to self-volume effect of silicon are suppressed. The cathode is stable after several infix and desfix of lithium ions, and cyclic stability and capacity retentivity of the pure silicon cathode are remarkably improved. In addition, the manufacturing method of the cathode is simple and accordant with requirements of industrial mass production and has high commercial value.
Description
Technical field
The present invention relates to a kind of lithium ion battery of the silicium cathode based on carbon cloth barrier layer, belong to field of electrochemical batteries.
Background technology
Lithium ion battery is as energy storage devices, because its volume is little, lightweight, energy density is high, power output is high, operating voltage is high, memory-less effect, charge efficiency are high, have extended cycle life and environmental friendliness, the advantage such as fail safe is high, cost is low, thus occupy a big chunk share of Battery Market, cell phone, notebook computer, digital camera and a lot of portable electric appts are widely used.
But along with the development of electronics technology, people require more and more higher to the energy density of lithium ion battery, such as, it is increasing that the screen of smart mobile phone does, and power consumption also increases thereupon.The negative pole of the lithium ion battery of current commercialization is graphite cathode, and its Theoretical Mass specific capacity is 372mAh/g, is difficult to the requirement meeting high capacity density.Found by researcher, when silicon is as electrode active material, its theoretical specific capacity is 4200mAh/g, it is 10 times more than of commercial graphite negative pole, but silicon materials have a fatal defect, are exactly in discharge process, the volumetric expansion very large (>300%) of himself, the thickness of cathode pole piece can be caused to increase on the one hand, cause the volume of negative pole to become large; The bulk effect of silicon can cause silicon to be easy to come off from collector on the other hand, causes the problem such as self discharge and short circuit.So the cycle performance of silicium cathode is very bad, and capacity attenuation is very serious first.
In order to solve the volumetric expansion/blockage effect of silicon materials in charge and discharge process, researcher takes a variety of method, such as prepare silicon/carbon composite electrode material by doping carbon class material, graphene-supported silicon materials are adopted to prepare the combination electrode material with space net structure, choose inert substance has " Lantern Festival " structure combination electrode material by coated Si preparation, the silicon composite of preparation nanostructure, select different binding agents, improve the adhesion of active material and collector, adopt amorphous silicon materials and silicon materials are directly prepared the electrode material of film forming as binder free, these methods inhibit the bulk effect of silicon to a certain extent, thus improve the performance of its discharge and recharge, but the preparation technology of these composite materials is often very loaded down with trivial details, generally relate to the technological requirement such as HTHP and sealing, cause the power consumption of technique huge, be difficult to realize industrialized a large amount of production.
Summary of the invention
The object of the invention is to solve existing lithium ion battery negative capacity low and prepare the problem of loaded down with trivial details difficulty, a kind of lithium ion battery of the silicium cathode based on carbon cloth barrier layer is provided.
The object of the invention is to be achieved through the following technical solutions.
Based on the lithium ion battery of the silicium cathode on carbon cloth barrier layer, comprise silicon-containing active material negative pole, barrier film, electrolyte and metal lithium sheet, one deck carbon cloth is set between silicon-containing active negative material and barrier film as barrier layer.
The density of described carbon cloth is 155 ~ 175g/cm
3, its thickness is 0.33 ~ 0.36mm.
The preparation of negative pole:
Using silica flour or silicon-carbon mixture (quality of silicon accounts for 5 ~ 10% of the mixture quality) active material as negative pole; Be binding agent by 1-METHYLPYRROLIDONE (NMP) solution of active material, conductive agent and Kynoar (PVDF), mix with mass ratio 6 ~ 8:1 ~ 3:1 ~ 3 and obtain thick slurry; By viscous paste even spread on a current collector, then in the vacuum drying chamber of 50 ~ 100 DEG C, oven dry obtains negative pole.
The cleaning method of described carbon cloth is:
Carbon cloth is used respectively the dust technology of 15% ~ 20%, ultrasonic immersing washing 20 ~ 60 minutes under deionized water and ethanol room temperature.Then dry 12 ~ 48 hours are put in 50 DEG C of vacuum drying chambers.Dried carbon cloth plasma cleaner is to cleaning, and in cleaning process, operating voltage is set to 650V, and oxygen gas flow rate is set to 500mL/min.
Described conductive agent is vacuum 100 DEG C of dried conductive blacks (Super-P) or acetylene black.
Described collector comprises carbon cloth, Copper Foil.
Beneficial effect
1, the lithium ion battery of the silicium cathode based on carbon cloth barrier layer of the present invention, the existence on carbon cloth barrier layer itself does not affect electron conduction and the ionic conductivity of negative pole, functionally can increase the distance between positive pole and negative pole on the one hand, prevent the positive pole owing to causing during membrane ruptures from contacting with the direct of negative pole, improve the fail safe that battery uses, there is obvious protective action; On the other hand, carbon cloth itself belongs to the structure of spatial network shape, such structure has good toughness, the stress because silicon volumetric expansion brings can be absorbed, prevent caving in of electrode, improve battery charging and discharging performance, with the first discharge specific capacity of the current density discharge and recharge of 0.5C for 1524mAhg
-1, the specific discharge capacity of the 100th circulation is 1258mAhg
-1.
2, the lithium ion battery of the silicium cathode based on carbon cloth barrier layer of the present invention, the business carbon cloth that can directly buy of employing is as the barrier layer of negative electrode active material, be placed between negative electrode active material and barrier film, carbon cloth itself only needs to carry out simple process in early stage and can come into operation, without the need to the preparation process of complexity.Process equally very simple that barrier layer is added, without the need to changing the internal structure of active material, the one deck of covering thereon carbon cloth of direct macroscopic view, safe and reliable, control accurate, with low cost, thus have a good application prospect, meet the requirement of industrial mass production, there is conspicuousness using value.
Accompanying drawing explanation
Fig. 1 is the charge and discharge cycles figure of pure silicon electrode under 1C current density;
Fig. 2 is X-ray diffraction (XRD) image of micron silicon;
Fig. 3 is carbon cloth surface scan Electronic Speculum (SEM) image;
Fig. 4 is the half-cell structural representation based on carbon cloth barrier layer;
Fig. 5 is the pure silicon electrode 0.5C charge and discharge cycles figure after adding carbon cloth barrier layer;
Fig. 6 is the charging/discharging voltage-specific capacity curve of pure silicon electrode the 1st circulation under 0.5C current density after adding carbon cloth barrier layer, the 2nd circulation, the 10th circulation, the 50th circulation.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention will be further described.
Comparative example 1
The preliminary treatment of copper foil current collector:
Copper Foil (thickness 9 ~ 15 microns, one side be light face, and one side is mute face) is cut into certain size light is faced down be laid on clean glass plate, dries and can use under room temperature after repeatedly cleaning mute with ethanol.
Prepared by electrode:
Thick silica flour (micron silicon, 40 ~ 200 orders, purity 99.99%) is active material, and electrically conductive graphite (Super-P) is conductive agent, and the nmp solution of PVDF is binding agent, mixes with mass ratio 7:2:1.Get appropriate silica flour and put into high speed ball mill, it is per minute that 400 circles are set, run 12 hours.After ball milling, silica flour sealing is kept in Dark Place for subsequent use.Conductive agent to need to be positioned in 100 DEG C of vacuum drying chambers dry 24 hours before use.In the silica flour handled well, add quantitative Super-P in proportion continue grinding until mix, subsequently mixture be placed in glassware and proportionally add binding agent (binder content 5%).Material is placed on medium speed on magnetic stirring apparatus and stirs 6h after adding.The thick slurry that will obtain after stirring, brushes on mute of Copper Foil after treatment uniformly by it, active material layer at 150 microns, then in the vacuum drying chamber of 100 DEG C dry 24 hours for subsequent use.
Battery is assembled:
The Copper Foil being coated with electrode slurry is made the circular pole piece that diameter is 12mm, weigh pole piece weight and be placed in 100 DEG C of vacuum drying chambers and go out unnecessary moisture, obtain pure silicon negative pole.With diameter 12mm, the metal lithium sheet of thickness 1mm is to electrode.Take diameter as the nickel foam of 12mm be electrode support.Be that the Celgard film of 18mm is as barrier film with diameter.Choosing 1mol/L lithium hexafluoro phosphate is solute, solvent is the mixed liquor of ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) three, volume ratio is 1:1:1, dresses up CR2025 type button cell according to anode cover, Electrode, barrier film, the der group of lithium sheet to electrode, nickel foam, negative electrode casing.The assembling of whole battery is crossed into and is all completed in the glove box being full of argon gas.
Electrochemical property test:
Use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery, charging/discharging voltage scope is 0.01V to 1.5V, and front and back time of repose is 1min, and charging and discharging currents is 1C.Discovery take pure silicon as its initial discharge capacity of battery of active material is 2500mAhg
-1above, but second time discharge capacity but decay to 1600mAhg
-1, visible capacitance loss very serious, and after the 10th circulation, its discharge capacity fluctuates substantially at 100mAhg
-1left and right, as shown in Figure 1.Fig. 2 is the XRD image of micron silicon, scanning angle is 5 ~ 80 degree, sweeping speed is 8 degrees/min, known by contrast PDF card, the silicon that we use belongs to Prof. Du Yucang silicon, and its crystallite dimension is larger, so it is more obvious in the bulk effect of Lithium-ion embeding/deviate from process, over numerous cycles, the active material configuration on collector caves in gradually due to effect of stress, causes the rapid decay of capacity.
Embodiment 1
The preliminary treatment of copper foil current collector:
Copper Foil (thickness 9 ~ 15 microns, one side be light face, and one side is mute face) is cut into certain size light is faced down be laid on clean glass plate, dries and can use under room temperature after repeatedly cleaning mute with ethanol.
The preliminary treatment of carbon cloth:
First carbon cloth is cut into suitable size, then carbon cloth is used respectively the dust technology of 15% ~ 20%, deionized water and ethanol at room temperature ultrasonic immersing washing 20 ~ 60 minutes.Dry 12 ~ 48 hours are put in 50 DEG C of vacuum drying chambers after cleaning.After carbon cloth drying, its smooth being placed in plasma cleaner cleaned, in cleaning process, operating voltage is set to 650V, and oxygen gas flow rate is set to 500mL/min, and scavenging period is set to 5min, can be for subsequent use after cleaning.Fig. 3 is ESEM (SEM) image on carbon cloth surface.
Prepared by electrode:
Thick silica flour (micron silicon, 40 ~ 200 orders, purity 99.99%) is active material, and acetylene black is conductive agent, and the nmp solution of PVDF is binding agent, mixes with mass ratio 7:2:1.Get appropriate silica flour and put into high speed ball mill, it is per minute that 400 circles are set, run 12 hours.After ball milling, silica flour sealing is kept in Dark Place.Acetylene black to need to be positioned in 100 DEG C of vacuum drying chambers dry 24 hours before use.In the silica flour handled well, add quantitative Super-P in proportion continue grinding until mix, subsequently mixture be placed in glassware and proportionally add binding agent (binder content 5%).Material is placed on medium speed on magnetic stirring apparatus and stirs 6h after adding.The thick slurry that will obtain after stirring, brushes on mute of Copper Foil after treatment uniformly by it, active material layer at 150 microns, then in the vacuum drying chamber of 100 DEG C dry 24 hours for subsequent use.
Battery is assembled:
The Copper Foil being coated with electrode slurry is made the circular pole piece that diameter is 12mm, weigh pole piece weight and be placed in 100 DEG C of vacuum drying chambers and go out unnecessary moisture, obtain pure silicon negative pole; Carbon cloth after cleaning is made the disk (thickness 0.34mm) that diameter is 12mm and does barrier layer.With diameter 12mm, the metal lithium sheet of thickness 1mm is to electrode.Take diameter as the nickel foam of 12mm be electrode support.Be that the Celgard film of 18mm is as barrier film with diameter.Choosing 1mol/L lithium hexafluoro phosphate is solute, and solvent is the mixed liquor of ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) three, and volume ratio is 1:1:1.Be placed between cathode pole piece and barrier film on carbon cloth barrier layer, then cover metal lithium sheet and nickel foam, negative electrode casing, be assembled into CR2025 type button cell, battery structure as shown in Figure 4.The assembling of whole battery is crossed into and is all completed in the glove box being full of argon gas.
Electrochemical property test:
Use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery, charging/discharging voltage scope is 0.02V to 1.5V, and front and back time of repose is 1min, and charging and discharging currents is 0.5C.The discharge capacity first of discovery battery is 1524mAhg
-1, the specific discharge capacity of the 100th circulation is 1258mAhg
-1, as shown in Figure 5.For pure silicon electrode, behind interpolation carbon cloth barrier layer, battery is all greatly improved on cycle performance and capability retention.
Embodiment 2
The preliminary treatment of copper foil current collector:
Copper Foil (thickness 9 ~ 15 microns, one side be light face, and one side is mute face) is cut into certain size light is faced down be laid on clean glass plate, dries and can use under room temperature after repeatedly cleaning mute with ethanol.
The preliminary treatment of carbon cloth:
First carbon cloth is cut into suitable size, then carbon cloth is used respectively the dust technology of 15% ~ 20%, deionized water and ethanol at room temperature ultrasonic immersing washing 20 ~ 60 minutes.Dry 12 ~ 48 hours are put in 50 DEG C of vacuum drying chambers after cleaning.After carbon cloth drying, its smooth being placed in plasma cleaner cleaned, in cleaning process, operating voltage is set to 650V, and oxygen gas flow rate is set to 500mL/min, and scavenging period is set to 5min.Can be for subsequent use after cleaning.
Prepared by electrode:
Thick silica flour (micron silicon, 40 ~ 200 orders, purity 99.99%) is active material, and Super-P is conductive agent, and the nmp solution of PVDF is binding agent, mixes with mass ratio 8:1:1.Get appropriate silica flour and put into high speed ball mill, it is per minute that 500 circles are set, run 24 hours.After ball milling, silica flour sealing is kept in Dark Place.Super-P to need to be positioned in 100 DEG C of vacuum drying chambers dry 24 hours before use.In the silica flour handled well, add quantitative acetylene black in proportion continue grinding until mix, subsequently mixture be placed in glassware and proportionally add binding agent (binder content 5%).Material is placed on medium speed on magnetic stirring apparatus and stirs 12h after adding.The thick slurry that will obtain after stirring, it brushed on mute of Copper Foil after treatment uniformly, active material layer is at 150 microns.Then in the vacuum drying chamber of 100 DEG C dry 24 hours for subsequent use.
Battery is assembled:
The Copper Foil being coated with electrode slurry is made the circular pole piece that diameter is 12mm, weigh pole piece weight and be placed in 100 DEG C of vacuum drying chambers and go out unnecessary moisture, obtain pure silicon negative pole; Carbon cloth after cleaning is made the disk (thickness 0.34mm) that diameter is 12mm and does barrier layer.With diameter 12mm, the metal lithium sheet of thickness 1mm is to electrode.Take diameter as the nickel foam of 12mm be electrode support.Be that the Celgard film of 18mm is as barrier film with diameter.Choosing 1mol/L lithium hexafluoro phosphate is solute, and solvent is the mixed liquor of ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) three, and volume ratio is 1:1:1.Carbon cloth barrier layer is placed between cathode pole piece and barrier film, then covers metal lithium sheet and nickel foam, negative electrode casing, be assembled into CR2025 type button cell.The assembling of whole battery is crossed into and is all completed in the glove box being full of argon gas.
Electrochemical property test:
Use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery, charging/discharging voltage scope is 0.02V to 2.0V, and front and back time of repose is 1min, and charging and discharging currents is 0.5C.Find that the first discharge specific capacity of battery is 2340mAhg behind interpolation carbon cloth barrier layer
-1, the specific discharge capacity after the 60th circulation is 1483mAhg
-1.Fig. 6 is the charging/discharging voltage-specific capacity curve of battery in the 1st circulation, the 2nd circulation, the 10th circulation, the 50th circulation, find that the voltage platform of discharge and recharge is stablized, and the decay of its charging and discharging capacity progressively reduces, and tends towards stability gradually.
Embodiment 3
The preliminary treatment of copper foil current collector:
Copper Foil (thickness 9 ~ 15 microns, one side be light face, and one side is mute face) is cut into certain size light is faced down be laid on clean glass plate, dries and can use under room temperature after repeatedly cleaning mute with ethanol.
The preliminary treatment of carbon cloth:
First carbon cloth is cut into suitable size, then carbon cloth is used respectively the dust technology of 15% ~ 20%, deionized water and ethanol at room temperature ultrasonic immersing washing 20 ~ 60 minutes.Dry 12 ~ 48 hours are put in 50 DEG C of vacuum drying chambers after cleaning.After carbon cloth drying, its smooth being placed in plasma cleaner cleaned, in cleaning process, operating voltage is set to 650V, and oxygen gas flow rate is set to 500mL/min, and scavenging period is set to 5min.Can be for subsequent use after cleaning.
The preparation of active material:
By thick silica flour (micron silicon, 40 ~ 200 orders, purity 99.99%) mix with 3000 order commercial graphite powder (purity 99.95%), the quality of silicon accounts for 6% of mixture gross mass, mixture is put into high speed ball mill and carries out ball milling, it is per minute that 400 circles are set, runs 12 hours.Taking out silicon/carbon mix after ball milling, to be placed in 80 DEG C of vacuum drying chambers for subsequent use.
Prepared by electrode:
Silicon/carbon composite is active material, and Super-P is conductive agent, and the nmp solution of PVDF is binding agent, mixes with mass ratio 8:1:1.Super-P to need to be positioned in 100 DEG C of vacuum drying chambers dry 24 hours before use.In silicon/carbon composite, add quantitative Super-P in proportion continue grinding until mix, subsequently mixture be placed in glassware and proportionally add binding agent (binder content 5%).Material is placed on medium speed on magnetic stirring apparatus and stirs 12h after adding.The thick slurry that will obtain after stirring, brushes on mute of Copper Foil after treatment uniformly by it, then in the vacuum drying chamber of 100 DEG C dry 24 hours for subsequent use.
Battery is assembled:
The Copper Foil being coated with electrode slurry is made the circular pole piece that diameter is 12mm, weigh pole piece weight and be placed in 100 DEG C of vacuum drying chambers and go out unnecessary moisture, obtain pure silicon negative pole; Carbon cloth after cleaning is made the disk (thickness 0.35mm) that diameter is 12mm and does barrier layer.With diameter 12mm, the metal lithium sheet of thickness 1mm is to electrode.Take diameter as the nickel foam of 12mm be electrode support.Be that the Celgard film of 18mm is as barrier film with diameter.Choosing 1mol/L lithium hexafluoro phosphate is solute, and solvent is the mixed liquor of ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) three, and volume ratio is 1:1:1.Carbon cloth barrier layer is placed between cathode pole piece and barrier film, then covers metal lithium sheet and nickel foam, negative electrode casing, be assembled into CR2025 type button cell.The assembling of whole battery is crossed into and is all completed in the glove box being full of argon gas.
Electrochemical property test:
The indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument is used to carry out charge-discharge test to battery, charging/discharging voltage scope is 0.02V to 2.0V, front and back time of repose is 1min, charging and discharging currents is 0.5C (the siliceous amount in silicon-carbon compound of getting, to calculate charging and discharging currents, calculates charging and discharging capacity with gross mass).Find the silicon-carbon combination electrode adding carbon cloth barrier layer, its first discharge specific capacity reaches 4790mAhg
-1, initial charge specific capacity is 3247mAhg
-1, the specific discharge capacity 1933mAhg of the 100th circulation
-1.
Embodiment 4
The preliminary treatment of carbon cloth:
First carbon cloth is cut into suitable size, then carbon cloth is used respectively the dust technology of 15% ~ 20%, deionized water and ethanol at room temperature ultrasonic immersing washing 20 ~ 60 minutes.Dry 12 ~ 48 hours are put in 50 DEG C of vacuum drying chambers after cleaning.After carbon cloth drying, its smooth being placed in plasma cleaner cleaned, in cleaning process, operating voltage is set to 650V, and oxygen gas flow rate is set to 500mL/min, and scavenging period is set to 5min.Can be for subsequent use after cleaning.
Prepared by electrode:
Thick silica flour (micron silicon) is active material, and Super-P is conductive agent, and the nmp solution of PVDF is binding agent, mixes with mass ratio 7:2:1.Get appropriate silica flour and put into high speed ball mill, it is per minute that 400 circles are set, run 12 hours.After ball milling, silica flour sealing is kept in Dark Place.Super-P to need to be positioned in 100 DEG C of vacuum drying chambers dry 24 hours before use.In the silica flour handled well, add quantitative Super-P in proportion continue grinding until mix, subsequently mixture be placed in glassware and proportionally add binding agent (binder content 5%).Material is placed on medium speed on magnetic stirring apparatus and stirs 6h after adding.The thick slurry that will obtain after stirring, brushes on carbon cloth collector after treatment uniformly by it, then in the vacuum drying chamber of 100 DEG C dry 24 hours for subsequent use.
Battery is assembled:
The carbon cloth being coated with electrode slurry is made the circular pole piece that diameter is 12mm, weigh pole piece weight and be placed in 100 DEG C of vacuum drying chambers and go out unnecessary moisture, obtain pure silicon negative pole; Carbon cloth after cleaning is made the disk (thickness 0.33mm) that diameter is 12mm and does barrier layer.With diameter 12mm, the metal lithium sheet of thickness 1mm is to electrode.Take diameter as the nickel foam of 12mm be electrode support.Be that the Celgard film of 18mm is as barrier film with diameter.Choosing 1mol/L lithium hexafluoro phosphate is solute, and solvent is the mixed liquor of ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) three, and volume ratio is 1:1:1.Carbon cloth barrier layer is placed between cathode pole piece and barrier film, then covers metal lithium sheet and nickel foam, negative electrode casing, be assembled into CR2025 type button cell.The assembling of whole battery is crossed into and is all completed in the glove box being full of argon gas.
Electrochemical property test:
Use the indigo plant of Wuhan Lan Bo Electronics Co., Ltd. electricity LANDCT2001A discharge and recharge instrument to carry out charge-discharge test to battery, charging/discharging voltage scope is 0.02V to 2.0V, and front and back time of repose is 1min, and charging and discharging currents is 0.5C.Find to add behind carbon cloth barrier layer, and be the pure silicon electrode of collector with carbon cloth, its first discharge specific capacity is 2674mAhg
-1, initial charge specific capacity is 2348mAhg
-1, after the 10th circulation, capacity dimension is held in 1539mAhg
-1, the specific discharge capacity of the 100th circulation is 1361mAhg
-1, reduce 0.128% from the 10th circle to the average specific capacity of often enclosing of the 100th circle.
Claims (6)
1. based on the lithium ion battery of the silicium cathode on carbon cloth barrier layer, comprise silicon-containing active material negative pole, barrier film, electrolyte and metal lithium sheet, it is characterized in that: one deck carbon cloth is set between silicon-containing active negative material and barrier film as barrier layer.
2., as claimed in claim 1 based on the lithium ion battery of the silicium cathode on carbon cloth barrier layer, it is characterized in that: the density of described carbon cloth is 155 ~ 175g/cm
3, its thickness is 0.33 ~ 0.36mm.
3. as claimed in claim 1 based on the lithium ion battery of the silicium cathode on carbon cloth barrier layer, it is characterized in that: the preparation method of described negative pole is: using silica flour or silicon-carbon mixture (quality of silicon accounts for 5 ~ 10% of the mixture quality) active material as negative pole; Be binding agent by the 1-METHYLPYRROLIDONE solution of active material, conductive agent and Kynoar, mix with mass ratio 6 ~ 8:1 ~ 3:1 ~ 3 and obtain thick slurry; By viscous paste even spread on a current collector, then in the vacuum drying chamber of 50 ~ 100 DEG C, oven dry obtains negative pole.
4. as claimed in claim 1 based on the lithium ion battery of the silicium cathode on carbon cloth barrier layer, it is characterized in that: the cleaning method of described carbon cloth is: carbon cloth is used respectively the dust technology of 15% ~ 20%, ultrasonic immersing washing 20 ~ 60 minutes under deionized water and ethanol room temperature; Then dry 12 ~ 48 hours are put in 50 DEG C of vacuum drying chambers; Dried carbon cloth plasma cleaner is to cleaning, and in cleaning process, operating voltage is set to 650V, and oxygen gas flow rate is set to 500mL/min.
5., as claimed in claim 1 based on the lithium ion battery of the silicium cathode on carbon cloth barrier layer, it is characterized in that: described conductive agent is vacuum 100 DEG C of dried conductive blacks or acetylene black.
6., as claimed in claim 1 based on the lithium ion battery of the silicium cathode on carbon cloth barrier layer, it is characterized in that: described collector comprises carbon cloth, Copper Foil.
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| CN105633346A (en) * | 2016-04-01 | 2016-06-01 | 中国科学技术大学 | Silicon anode of lithium-ion battery and preparation method of silicon anode and lithium-ion battery |
| CN105680065A (en) * | 2016-04-13 | 2016-06-15 | 唐海涛 | Lithium battery with carbon fiber cloth barrier layer |
| CN111446415A (en) * | 2020-04-13 | 2020-07-24 | 珠海冠宇电池股份有限公司 | Silicon negative plate and preparation method and application thereof |
| CN115616054A (en) * | 2022-10-29 | 2023-01-17 | 福州大学 | Preparation method of silicon-based composite photoelectrode |
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| CN104716382A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Lithium-sulfur battery structure |
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| CN105633346A (en) * | 2016-04-01 | 2016-06-01 | 中国科学技术大学 | Silicon anode of lithium-ion battery and preparation method of silicon anode and lithium-ion battery |
| CN105680065A (en) * | 2016-04-13 | 2016-06-15 | 唐海涛 | Lithium battery with carbon fiber cloth barrier layer |
| CN111446415A (en) * | 2020-04-13 | 2020-07-24 | 珠海冠宇电池股份有限公司 | Silicon negative plate and preparation method and application thereof |
| CN115616054A (en) * | 2022-10-29 | 2023-01-17 | 福州大学 | Preparation method of silicon-based composite photoelectrode |
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