CN105742575B - A kind of method that polyvinyl alcohol crosslinked carbonization of gelatin in situ prepares the porous silicium cathode of lithium ion battery - Google Patents
A kind of method that polyvinyl alcohol crosslinked carbonization of gelatin in situ prepares the porous silicium cathode of lithium ion battery Download PDFInfo
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- CN105742575B CN105742575B CN201610157766.XA CN201610157766A CN105742575B CN 105742575 B CN105742575 B CN 105742575B CN 201610157766 A CN201610157766 A CN 201610157766A CN 105742575 B CN105742575 B CN 105742575B
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- polyvinyl alcohol
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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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
- H01M4/366—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—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
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 present invention proposes a kind of method that polyvinyl alcohol crosslinked carbonization of gelatin in situ prepares the porous silicium cathode of lithium ion battery, mix to obtain cross-linked binder using by polyvinyl alcohol and gelatin, cross-linked binder will be added after silicon materials and conductive agent ground and mixed, after grinding uniformly with scraper for coating on copper foil, dry in an oven, it is placed in tube furnace and is calcined under an inert atmosphere, porous silicium cathode is obtained after cooling.Present invention selection gelatin and polyvinyl alcohol crosslinked conduct binding agent use, and porous silicium cathode is made, by being further carbonized, removes most of organic matter, while improve the electric conductivity of electrode, effectively improve the chemical property of silicon materials.The present invention is safe and non-toxic, and preparation is simple, and the porous silicon negative electrode material being prepared shows higher specific capacity and good cyclical stability as lithium ion battery negative material.
Description
Technical field
The present invention relates to a kind of environment-friendly lithium ion battery preparation method of porous silicon negative electricity pole piece, belonging to
Work electrode material manufacturing process technology field.Preparation method of the embodiment of the present invention is simple, easy to operate, reproducible, and cost is cheap,
It is environmentally safe.
Background technology
A large amount of releases of harmful substance in continuous consumption and its consumption process in face of non-renewable energy resources, research and develop and efficient
It is extremely urgent using clean energy resource.In new energy field, lithium ion battery because having high-energy-density, high working voltage, follow by length
The advantages that ring life-span and memory-less effect and be widely used in multiple fields, such as portable mobile apparatus, electric automobile, energy storage
Power station etc..However, as job requirement of the market to electric equipment improves constantly, the energy density of lithium ion battery, power are close
Degree, cycle life and security can not meet the needs of market substantially.
Important component of the electrode material as lithium ion battery, its performance are also required to further improve.At present, business
With negative pole is changed mainly based on graphite, its theoretical capacity only has 372mAhg-1, lithium ion battery high-energy-density can not be met
Demand for development.For silicon materials as one of current numerous alternative lithium ion battery negative materials, it has theoretical specific capacity height
(~4200mAhg-1), suitable operating potential (<0.5V vs.Li/Li+), rich reserves and advantages of environment protection, draw
The extensive concern of scholars is played.However, silicon materials are faced with a urgent problem to be solved, i.e. silicon materials in actual applications
Violent Volume Changes (~400%) can occur during removal lithium embedded repeatedly, cause the electrical contact of electrode to deteriorate, material powder
Change and SEI films excess growth, cause battery capacity decline rapidly and coulombic efficiency reduce.At present, reduction is mainly passed through
The particle diameter of silicon grain, in silicon grain coated with carbon, and prepare silicon/carbon complex these three methods and be modified.Prepare silicon
Composite is come to alleviate the volumetric expansion of silicon materials be a kind of relatively effective method, but the preparation process ratio of such method of modifying
It is more complicated.
For PVDF as commercialization binding agent, it has acceptable viscosity and wide electrochemical window, but has needed to use
Solvents of the NMP of poison as PVDF, PVDF is the direct coupled structure without functional group in addition, is only capable of by weaker Van der Waals force
Combined with silicon, can not play a part of suppress silicon materials volumetric expansion, and its can gelation or dissolving in organic electrolyte, because
This, the binding agent that PVDF is not suitable as silicon materials uses.Gelatin is big as commercial, inexpensive, environment-friendly water-soluble biological
Molecule, because with carboxyl and amino and with preferable adhesiveness, being used frequently as surfactant and dispersant, and its is insoluble
In conventional organic electrolyte, thus can be used as the binding agent of silicon materials.Polyvinyl alcohol is also a kind of environment-friendly water
Insoluble macromolecular, there are many hydroxyls in its chain structure, the network of crosslinking with cross linking of gelatin, can be generated.Using big
Molecule gets up silicon materials cladding, generates the cross-linked network of loose structure, is effectively improved contact of the silicon materials with electrolyte
Area, it is more beneficial for the transmission of lithium ion；Organic matter is carried out again partially carbonized, the electric conductivity of silicon electrode can be effectively improved
Energy.The present invention relates to a kind of method for preparing the porous silicium cathode of lithium ion battery using gelatin in situ-polyvinyl alcohol crosslinked carbonization.
The content of the invention
The invention aims to improve the chemical property of lithium ion battery silicium cathode material, electrode slice system is improved
Environment friendly during standby, reduces the requirement to humidity in preparation process, and a kind of gelatin-polyvinyl alcohol in situ proposed
The method that cross-linking carbonization prepares the porous silicium cathode of lithium ion battery.
The purpose of the present invention is achieved through the following technical solutions.
The method that a kind of gelatin in situ-polyvinyl alcohol crosslinked carbonization prepares the porous silicium cathode of lithium ion battery, specific steps
It is as follows：
1) polyvinyl alcohol is dissolved in deionized water, heating stirring dissolving；
2) gelatin is added in the solution obtained to step 1), heating stirring dissolving, obtains cross-linked binder, wherein gelatin
Mass ratio with polyvinyl alcohol is 1:1~0.1:1；
3) by after silica flour and conductive agent ground and mixed, the cross-linked binder that step 2) obtains, wherein silicon are added into mortar
The mass ratio of powder, polyvinyl alcohol+gelatin and conductive agent is 6:3:1 or 6:2:2, after grinding uniformly with scraper for coating on copper foil,
Vacuum drying in an oven, obtain electrode slice；
4) electrode slice obtained in step 3) is placed in tube furnace and calcined under an inert atmosphere, 200~300
Precalcining 1~2 hour at DEG C, then calcined 1~2 hour at 300 DEG C~600 DEG C, after reaction terminates, under inert atmosphere protection
Room temperature is cooled to, obtains porous silicium cathode.
Conductive agent described in step 3) is one or more of mixed in Super-P, acetylene black, graphite or CNT
Close；
Drying temperature is 30 DEG C~60 DEG C in baking oven described in step 3)；
Beneficial effect
1st, present invention selection gelatin and polyvinyl alcohol crosslinked conduct binding agent use, and porous silicium cathode are made, by entering one
Step carbonization, removes most of organic matter, while improves the electric conductivity of electrode, effectively improves the chemical property of silicon materials.
Constant current charge-discharge test is carried out to lithium-ion button battery prepared by the porous silicon negative electricity pole piece, it shows high discharge and recharge
Specific capacity and good cycle performance：0.1C (400mA·g-1) under the conditions of circulate 50 weeks, capacity is maintained at 1100mAhg-1
Left and right.
2nd, the present invention is safe and non-toxic, and preparation is simple, and the silicium cathode electrode slice for preparing gained has loose structure,
Gelatin/polyvinyl alcohol occurs partially carbonized after calcining, and the introducing of wherein carbon effectively increases the electric conductivity of silicium cathode, hands over simultaneously
Network of networking provides certain buffering inhibitory action to the Volume Changes of silicon materials, and loose structure adds electrolyte and electrode material
Contact area, be more beneficial for the transmission of lithium ion.This porous silicon negative electrode material is as lithium ion battery negative material table
Reveal higher specific capacity and good cyclical stability.
Brief description of the drawings
Fig. 1 is the SEM shape appearance figures of porous silicon negative electricity pole piece prepared by embodiment 1, and a is the material do not calcined, b 500
Material after being calcined at DEG C；
Fig. 2 is the porous silicon negative material of different calcining heats prepared by embodiment 1 in 400mA g-1Under discharge and recharge
Specific capacity change curve.
Embodiment
The present invention is elaborated with reference to embodiment and accompanying drawing.
Embodiment 1
The method that a kind of gelatin in situ-polyvinyl alcohol crosslinked carbonization prepares the porous silicium cathode of lithium ion battery, specific steps
For：
1) 60mg polyvinyl alcohol is dissolved in 4ml deionized waters, heating stirring dissolves at 80 DEG C；
2) 60mg gelatin is added in the solution obtained to step 1), heating stirring dissolves at 60 DEG C, obtains cross-linked binder
Agent；
3) by after 240mg silica flours and 40mg Super-P ground and mixeds, the crosslinking that addition step 2) obtains into mortar is glued
Agent is tied, after grinding uniformly with scraper for coating on copper foil, 60 DEG C of vacuum dryings, obtain electrode slice in an oven, and its SEM pattern is such as
Shown in Fig. 1 a；
4) electrode slice obtained in step 3) is placed in tube furnace and calcined under an argon atmosphere, it is pre- at 300 DEG C
Calcining 2 hours, then calcined 1.5 hours at 500 DEG C, after reaction terminates, room temperature is cooled under argon gas atmosphere protection, is handed over
The porous silicium cathode of connection, the obtained SEM patterns of silicium cathode are calcined at 500 DEG C as shown in Figure 1 b.
Embodiment 2
The method that a kind of gelatin in situ-polyvinyl alcohol crosslinked carbonization prepares the porous silicium cathode of lithium ion battery, specific steps
For：
1) 40mg polyvinyl alcohol is dissolved in 2ml deionized waters, heating stirring dissolves at 80 DEG C；
2) 40mg gelatin is added in the solution obtained to step 1), heating stirring dissolves at 60 DEG C, obtains cross-linked binder
Agent；
3) by after 240mg silica flours and 80mg Super-P ground and mixeds, the crosslinking that addition step 2) obtains into mortar is glued
Agent is tied, after grinding uniformly with scraper for coating on copper foil, 60 DEG C of vacuum dryings, obtain electrode slice in an oven；
4) electrode slice obtained in step 3) is placed in tube furnace and calcined under an argon atmosphere, it is pre- at 300 DEG C
Calcining 2 hours, then calcined 2 hours under 400 0 C, after reaction terminates, room temperature is cooled under argon gas atmosphere protection, is handed over
The porous silicium cathode of connection.
Embodiment 3
The method that a kind of gelatin in situ-polyvinyl alcohol crosslinked carbonization prepares the porous silicium cathode of lithium ion battery, specific steps
For：
1) 80mg polyvinyl alcohol is dissolved in 4ml deionized waters, heating stirring dissolves at 80 DEG C；
2) 40mg gelatin is added in the solution obtained to step 1), heating stirring dissolves at 60 DEG C, obtains cross-linked binder
Agent；
3) by after 240mg silica flours and 40mg CNT ground and mixeds, the crosslinking that addition step 2) obtains into mortar is glued
Agent is tied, after grinding uniformly with scraper for coating on copper foil, 60 DEG C of vacuum dryings, obtain electrode slice in an oven；
4) electrode slice obtained in step 3) is placed in tube furnace and calcined under an argon atmosphere, it is pre- at 300 DEG C
Calcining 2 hours, then calcined 1 hour at 600 DEG C, after reaction terminates, room temperature is cooled under argon gas atmosphere protection, is crosslinked
Porous silicium cathode.
Using the porous silicon negative electricity pole piece that embodiment 1 obtains as working electrode, lithium metal be to electrode, 1mol/L's
LiF6/ EC-DMC (volume ratio 1: 1) is electrolyte, after lithium ion half-cell is assembled into argon gas atmosphere glove box, carries out electricity
Chemical property is tested, and voltage range is 0.01~1.5V (vs.Li+/ Li), current density 400mAg-1。
Test result：600 DEG C are calcined obtained porous silicium cathode in 400mAg-1Charging and discharging capacity becomes during lower discharge and recharge
Changing curve, (embedding lithium) specific capacity and charging (de- lithium) specific capacity are respectively 1508.7mAhg as shown in Fig. 2 it discharges first-1、
1164.1mAh·g-1, its electric discharge (embedding lithium) specific capacity and charging (de- lithium) specific capacity are respectively 1157.2mAh after circulating 50 weeks
g-1、1126.5mAh·g-1。
Claims (3)
1. the method that a kind of gelatin in situ-polyvinyl alcohol crosslinked carbonization prepares the porous silicium cathode of lithium ion battery, it is characterised in that
Comprise the following steps that：
1) polyvinyl alcohol is dissolved in deionized water, heating stirring dissolving；
2) gelatin is added in the solution obtained to step 1), heating stirring dissolving, obtains cross-linked binder, wherein gelatin is with gathering
The mass ratio of vinyl alcohol is 1:1~0.1:1；
3) after silica flour and conductive agent ground and mixed the obtained cross-linked binder of step 2) will be added into mortar, wherein silica flour, poly-
The mass ratio of vinyl alcohol+gelatin and conductive agent is 6:3:1 or 6:2:2, after grinding uniformly with scraper for coating on copper foil, in baking oven
Middle vacuum drying, obtains electrode slice；
4) electrode slice obtained in step 3) is placed in tube furnace and calcined under an inert atmosphere, it is pre- at 200~300 DEG C
Calcining 1~2 hour, then calcined 1~2 hour at 300 DEG C~600 DEG C, after reaction terminates, it is cooled under inert atmosphere protection
Room temperature, obtain porous silicium cathode.
2. the method as described in claim 1, it is characterised in that：Conductive agent described in step 3) is Super-P, acetylene black, stone
One or more of mixing in ink or CNT.
3. the method as described in claim 1, it is characterised in that：Drying temperature is 30 DEG C~60 in baking oven described in step 3)
℃。
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| CN106229487A (en) * | 2016-08-25 | 2016-12-14 | 北京化工大学 | The method of lithium-sulfur cell charcoal/lithium sulfide composite positive pole prepared by a kind of carbon thermal reduction lithium sulfate |
| CN108511740A (en) * | 2017-03-13 | 2018-09-07 | 万向二三股份公司 | A kind of high-specific-capacity silicon carbon electrode coating preparation method |
| CN108335800B (en) * | 2017-12-29 | 2020-12-11 | 天津工业大学 | Copper-silicon integrated electrode and preparation method thereof |
| JP7093505B2 (en) * | 2018-08-08 | 2022-06-30 | トヨタ自動車株式会社 | A positive electrode for a lithium ion capacitor, a lithium ion capacitor using the positive electrode, and a method for manufacturing them. |
| US20200227728A1 (en) * | 2019-01-16 | 2020-07-16 | GM Global Technology Operations LLC | Methods of making high performance electrodes |
| CN110299511B (en) * | 2019-05-27 | 2020-10-09 | 南方科技大学 | Nano composite negative plate, preparation method thereof and lithium ion battery |
| CN111244454A (en) * | 2019-10-10 | 2020-06-05 | 江苏正力新能电池技术有限公司 | High-proportion silicon cathode water system composite binder and application thereof |
| CN112038631A (en) * | 2020-09-03 | 2020-12-04 | 青海凯金新能源材料有限公司 | Lithium battery electrode plate with surface coated with natural graphite and processing technology thereof |
| CN114975943B (en) * | 2022-06-08 | 2023-06-16 | 陕西科技大学 | Preparation method for constructing gelatin/silicon nanoparticle microspheres based on emulsification self-assembly method |
| CN114975944B (en) * | 2022-06-08 | 2023-08-29 | 陕西科技大学 | Silicon-carbon negative electrode material with high-strength carbon matrix and preparation method thereof |
| CN114975942B (en) * | 2022-06-08 | 2023-06-13 | 陕西科技大学 | Micro/nano structure silicon-carbon negative electrode material and preparation method thereof |
| CN116190660B (en) * | 2023-03-10 | 2024-01-30 | 南京航空航天大学 | Adhesive, preparation method and application thereof, silicon-based negative electrode and preparation method thereof |
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