A kind of method of being prepared lithium battery by garlic or onion
Technical field
The present invention relates to a kind of method of being prepared lithium battery by garlic or onion, belong to lithium ion battery material technology of preparing and application thereof.
Background technology
Lithium ion battery has that energy density is high, the feature of long service life, since 1991 put goods on the market, got most of the attention always, be widely used in middle-size and small-size field of batteries such as mobile phone, notebook computer, electric tool, electric bicycles, become an indispensable part in the 21 century economy of energy.But, in recent years, the rise of electric motor car, high-power, high-capacity secondary battery demand are increasingly sharpened, requirement to lithium ion battery material and lithium ion battery production technology is more and more higher, continually develop there is high storage density, safe and reliable, cheap lithium ion battery material, the one-step optimization production technology of going forward side by side etc. has become the developing direction of lithium ion battery industry.
Natural plant resource is abundanter, in prior art, there is the example of much being prepared by natural plant fibre to active carbon, as publication number (CN102 951635A) discloses a kind of method of utilizing wooden slag and tealeaves charing to prepare active carbon, its active carbon of preparing is mainly used to the moisture absorption, inhales taste.Fully, the plant such as garlic, onion has abundant string simultaneously, is rich in organic sulfur compound for the natural plants such as garlic, onion source.Galic essential oil is described as wide-spectrum bactericide, has the feature of integration of drinking and medicinal herbs, doctor food homology, and it is a kind of flavouring still not, has unique fragrant pungent, the more important thing is that it has broad-spectrum sterilization effect, due to the multiple effect in its pharmacology.Publication number (CN102311879A) discloses a kind of preparation method of galic essential oil, specifically adopts molecular clock separation and purification.If imagination can make full use of lithium battery field by plant resources abundant to garlic, onion etc., be of great significance for expansion battery material selection range, reduction material cost tool.
Summary of the invention
The object of the invention is to be to provide a kind of and utilize cheap natural plants for raw material, prepare high power capacity, the method for lithium ion battery cheaply by easy steps.
The invention provides a kind of method of being prepared lithium battery by garlic or onion, the method is taking garlic and/or onion as raw material, and garlic and/or onion epidermis are obtained to the active carbon as electrode conductive material by 550~650 DEG C of high temperature carbonizations; The meat of garlic and/or onion is obtained as the essential oil of binders for electrodes and/or liquid electrolyte material by alcohol extract; Described essential oil is further carried out to addition reaction with poly-methyl hydrogen-containing siloxane at 70~90 DEG C and obtain the modified polyorganosiloxane as solid electrolyte material; Or using described essential oil further at 55~65 DEG C of temperature crosslinking curing obtain the solidfied material as electrode active material; By one or more in the described active carbon making as raw material taking garlic and/or onion, essential oil, modified polyorganosiloxane, solidfied material, allocate other stock of preparing lithium battery into and be prepared into solid-state or liquid lithium battery.
The method of preparing lithium battery by garlic or onion of the present invention also comprises following preferred version.
In preferred method by the active carbon making using garlic and/or onion as raw material as electrode conductive material, the essential oil that makes as binders for electrodes and/or liquid electrolyte material, the modified polyorganosiloxane that makes as solid electrolyte material and the solidfied material that makes as electrode active material, allocate other stock of preparing lithium battery into and be prepared into solid-state or liquid lithium battery.Most preferably be the active carbon that makes using garlic as raw material as electrode conductive material, the essential oil that makes as binders for electrodes and as liquid electrolyte material and the solidfied material that makes as electrode active material, allocate other stock of preparing lithium battery into and be prepared into liquid lithium battery; Or the active carbon making using garlic as raw material as electrode conductive material, the essential oil that makes as binders for electrodes, the modified polyorganosiloxane that makes is as solid electrolyte material and the solidfied material that makes as electrode active material, allocate other stock of preparing lithium battery into and be prepared into solid state lithium battery.
The organic compounds containing sulfur of essential oil described in preferred method including allyl methyl thioether, allyl sulfide, allyl methyl disulfide, diallyl disulphide, allyl methyl trisulfide ether, Diallytrisin and Diallytrisin.
In preferred method, garlic and/or onion are removed epidermis, and pulp is smashed to pieces, at 55~65 DEG C, dry after moisture, grind, gained powder soaks 4~8h, suction filtration with ethanol at 40~50 DEG C, obtain extract, gained extract evaporate to dryness alcohol solvent, obtains essential oil.
In preferred method, garlic and/or onion epidermis are under inert atmosphere, and charing 18~30h under 550~650 DEG C of high temperature, obtains active carbon.
Described in preferred method, the time of crosslinking curing is 64~80h.
Essential oil and poly-methyl hydrogen-containing siloxane described in preferred method are dissolved in benzene kind solvent in 1:3~5 in mass ratio, at the temperature of 70~90 DEG C, react 20~28h, obtain modified polyorganosiloxane.
Described benzene kind solvent is toluene, dimethylbenzene etc.
Beneficial effect of the present invention: the present invention by straightforward procedure first using the natural plant raw material such as garlic, onion prepare electrodes conduct absorbent charcoal material, can be used as binders for electrodes and/or liquid electrolyte material essential oil, can be used as the modified polyorganosiloxane of solid electrolyte material and the solidfied material as electrode active material, select wherein one or more to allocate again other stock of preparing lithium battery into and be prepared into solid-state or liquid lithium battery; The conduction active-carbon, binding agent, electrolyte and the electrode active material that most preferably are in solid-state or liquid lithium battery are all to be prepared by garlic raw material, the lithium battery capacity that makes is large, good cycle, cost is low, has expanded range of choice and the application of lithium ion battery material.
Brief description of the drawings
The lithium battery cycle performance figure that [Fig. 1] makes for the embodiment of the present invention 1.
The lithium battery cycle performance figure that [Fig. 2] makes for the embodiment of the present invention 2.
Embodiment
Following examples are intended to further illustrate content of the present invention, instead of limit the scope of the invention.
Embodiment 1
By garlic peeling, smash into mashed garlic, put into baking oven, dry 6h at 60 DEG C, grinds, adds absolute ethyl alcohol, soaks 6h at 50 DEG C, suction filtration, clear liquid is allicin ethanol stoste, evaporate to dryness allicin solution obtains galic essential oil.The galic essential oil, the conductive black of 0.15g and the sublimed sulfur of 0.3g that take 0.05g, mix, and fully grinds.Batch mixing after dry grinding carries out wet-milling taking 1-METHYLPYRROLIDONE as solvent.Slurry after milled is coated on aluminium foil, at the temperature of 60 DEG C, is dried two days.Dried pole piece is cut into the disk that diameter is 1cm.Taking this disk as anodal, the polyoxyethylene solid electrolyte that metal organic frame is filler is electrolyte, and lithium sheet is negative pole, is assembled into button cell, carries out charge-discharge test.Battery at the cycle performance of 80 DEG C and 0.3C multiplying power as shown in Figure 1.
Embodiment 2
By garlic peeling, smash into mashed garlic, put into baking oven, dry 7h at 60 DEG C, grinds, adds absolute ethyl alcohol, soaks 6h at 45 DEG C, suction filtration, clear liquid is allicin ethanol stoste, evaporate to dryness allicin solution obtains galic essential oil.The poly-methyl hydrogen-containing siloxane of the galic essential oil of 0.5g and 2g is dissolved in toluene, and 80 DEG C of back flow reaction 26h, revolve evaporate to dryness by product dry, except desolventizing, obtain the polysiloxanes of galic essential oil modification.The LiTFSI of this polysiloxanes of 0.5g and 0.1g is dissolved in acetonitrile, uses solvent evaporation method to be prepared into copolymer solid electrolyte.Taking LiFePO4 as anodal, lithium sheet is negative pole, uses this electrolyte assembling button cell, carries out charge-discharge test.Battery at the cycle performance of 80 DEG C and 1C multiplying power as shown in Figure 2.
Embodiment 3
The epidermis of fresh garlic is placed in to tube furnace, under argon gas atmosphere, it is carried out to carbonization, temperature is 600 DEG C, and carbonization time is 24h, obtains black strip material.Get material, the Kynoar of 0.05g and the sublimed sulfur of 0.3g after the carbonization of 0.15g, mix and fully grind, after dry grinding, carry out wet-milling taking 1-METHYLPYRROLIDONE as solvent, the slurry after milled is coated on aluminium foil, at the temperature of 60 DEG C, is dried two days.Dried pole piece is cut into the disk that diameter is 1cm.Taking this disk as anodal, the polyoxyethylene solid electrolyte that metal organic frame is filler is electrolyte, and lithium sheet is negative pole, is assembled into button cell, carries out charge-discharge test, and battery is 830mAh g in the initial discharge specific capacity of 80 DEG C and the circulation of 0.3C multiplying power
-1.
Embodiment 4
The epidermis of fresh garlic is placed in to tube furnace, under argon gas atmosphere, it is carried out to carbonization, temperature is 600 DEG C, and carbonization time is 28h, obtains black strip material.With the method acquisition galic essential oil identical with embodiment 2, and be prepared into copolymer solid electrolyte.Get material, the Kynoar of 0.05g and the LiFePO4 of 0.3g after the carbonization of 0.15g, mix and fully grind, after dry grinding, carry out wet-milling taking 1-METHYLPYRROLIDONE as solvent, the slurry after milled is coated on aluminium foil, at the temperature of 60 DEG C, is dried two days.Dried pole piece is cut into the disk that diameter is 1cm.Taking this disk as anodal, the copolymer solid electrolyte of preparation is electrolyte, and lithium sheet is negative pole, is assembled into button cell, carries out charge-discharge test, and battery is 135mAh g in the initial discharge specific capacity of 80 DEG C and the circulation of 0.3C multiplying power
-1, after circulation 20 circles, capability retention is 99.5%.
Embodiment 5
By garlic peeling, smash into mashed garlic, put into baking oven, dry 8h at 60 DEG C, grinds, adds absolute ethyl alcohol, soaks 6h at 40 DEG C, suction filtration, clear liquid is allicin ethanol stoste, evaporate to dryness allicin solution obtains galic essential oil.Galic essential oil is placed in 60 DEG C and heats 72h, obtain solid product.This product, the Kynoar of 0.05g and the conductive black of 0.15g that take 0.3g, mix, and fully grinds.Batch mixing after dry grinding carries out wet-milling taking 1-METHYLPYRROLIDONE as solvent.Slurry after milled is coated on aluminium foil, at the temperature of 60 DEG C, is dried two days.Dried pole piece is cut into the disk that diameter is 1cm.Taking this disk as anodal, the polyoxyethylene solid electrolyte that metal organic frame is filler is electrolyte, and lithium sheet is negative pole, is assembled into button cell, carries out charge-discharge test, and battery is 310mAh g in the initial discharge specific capacity of 80 DEG C and the circulation of 0.3C multiplying power
-1, after circulation 20 circles, capability retention is 98.6%.
Embodiment 6
By garlic peeling, smash into mashed garlic, put into baking oven, dry 6h at 60 DEG C, grinds, adds absolute ethyl alcohol, soaks 6h at 50 DEG C, suction filtration, clear liquid is allicin ethanol stoste, evaporate to dryness allicin solution obtains galic essential oil.Galic essential oil is placed in 60 DEG C and heats 72h, obtain solid product, as electrode active material.The poly-methyl hydrogen-containing siloxane of the galic essential oil of 0.5g and 2g is dissolved in toluene, and 80 DEG C of back flow reaction 24h, revolve evaporate to dryness by product dry, except desolventizing, obtain the polysiloxanes of galic essential oil modification.The LiTFSI of this polysiloxanes of 0.5g and 0.1g is dissolved in acetonitrile, uses solvent evaporation method to be prepared into galic essential oil modified polyorganosiloxane solid electrolyte.The epidermis of fresh garlic is placed in to tube furnace, under argon gas atmosphere, it is carried out to carbonization, temperature is 600 DEG C, and carbonization time is 20h, obtains black strip material, as electrode conductive material.Active material, the galic essential oil of 0.05g and the electric conducting material of 0.15g of getting 0.3g, mix, and fully grinds.Batch mixing after dry grinding carries out wet-milling taking 1-METHYLPYRROLIDONE as solvent.Slurry after milled is coated on aluminium foil, at the temperature of 60 DEG C, is dried two days.Dried pole piece is cut into the disk that diameter is 1cm.Taking this disk as anodal, galic essential oil modified polyorganosiloxane solid electrolyte is electrolyte, and lithium sheet is negative pole, is assembled into button cell, carries out charge-discharge test, and battery approaches 300mAh g in the initial discharge specific capacity of 80 DEG C and the circulation of 0.3C multiplying power
-1, after circulation 20 circles, capability retention is 98.8%.