CN101847764A - High-specific-energy/high-specific-power type super battery - Google Patents
High-specific-energy/high-specific-power type super battery Download PDFInfo
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- CN101847764A CN101847764A CN201010114605A CN201010114605A CN101847764A CN 101847764 A CN101847764 A CN 101847764A CN 201010114605 A CN201010114605 A CN 201010114605A CN 201010114605 A CN201010114605 A CN 201010114605A CN 101847764 A CN101847764 A CN 101847764A
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Abstract
The invention relates to a high-specific-energy/high-specific-power type super battery, consisting of a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode, and organic electrolyte, wherein the positive electrode is formed by parallel connection of two types of electrode pieces, i.e. an electrode piece which adopts a lithium-ion-embedded compound in a lithium ion battery as an active material and an electrode piece of a porous carbon material in a double electric layer super capacitor, the negative electrode adopts a negative electrode carbon material of the lithium ion battery, and the electrolyte is of an organic solvent containing lithium ion salt electrolyte. The high-specific-energy/high-specific-power type super battery has high energy density and power density simultaneously, wherein the specific energy can be up to 50-110wh/kg, and the power density can be up to 450-8000w/kg; and the high-specific-energy/high-specific-power type super battery can be widely applied in the fields such as electric automobiles, electric tools, solar energy storage, wind energy storage, portable household appliances and the like.
Description
Technical field
The present invention relates to the battery technology field, particularly relate to a kind of high-energy-density/high-specific-power type super battery.
Background technology
Natural resources such as the coal of use, oil, natural gas are exhausted day by day on a large scale always along with the mankind, and problems such as energy crisis and shortage of resources become increasingly conspicuous.Meanwhile, the environmental problem brought of the pernicious gas that discharged of natural calculus-dissolving energy burning also becomes the key factor of restriction human social development day by day.Therefore make full use of the existing energy, exploitation environmental protection new forms of energy and correlation technique thereof, the person that becomes the current research the problem that will urgently solve.Wherein, be that the energy of representative stores with the conversion field and becomes one of focus of research with lithium rechargeable battery and ultracapacitor.Lithium rechargeable battery has that volume is little, in light weight, operating voltage is high, specific energy is big, memory-less effect, advantage such as pollution-free; Ultracapacitor has that power density height, high current charge-discharge ability are strong, numerous advantages such as have extended cycle life.The energy device of two kinds of environment-friendly and greens has obtained using widely in various fields such as information industry, energy traffic through the research of every industry or trade and researcher many decades.But because the shortcoming that lithium rechargeable battery exists that power density is low, cycle life is short, ultracapacitor then exists the not high shortcoming of energy density, has seriously restricted both application at some special dimensions.In order to overcome this two kinds of defectives that the novel energy device brings, researcher is all actively being sought a kind of new energy device of exploitation, thereby obtains the more good novel energy device of a kind of performance with the advantage in conjunction with both of hoping.
At present the mode that ultracapacitor and these two kinds of energy storage systems of secondary cell are combined has two kinds, a kind ofly is " outer in conjunction with " formula (soon both monomers are combined into an energy storage component or system by power-supply management system); Another kind is " interior combination " formula (being about to both organically is combined in the same monomer).The hybrid power source system that composes in parallel by ultracapacitor and storage battery (" outer in conjunction with " formula power-supply system), though can obtain the power of electric automobile, because of have that specific power is low, weight and volume is excessive and system management and control too complicated not ideal enough." interior combination " formula power-supply system has the specific power height, weight and volume is little, cost is low, guarantees the consistency of monomer easily, reduces the complexity of management system, therefore, becomes the emphasis of current research.
This type of organic hybrid super capacitor, because both positive and negative polarity all introduced, at temperature higher (greater than 40 ℃ time), electrolyte decomposition was serious when monomer voltage was higher than 3.6V, had limited its large-scale application.In recent years, Japan capacitor manufacturer numerous and confused development a kind of new ultracapacitor---mixed type lithium ion super capacitor, the anodal pole piece that adopts traditional double electric layer capacitor, wherein the most frequently used is the active carbon pole piece, it is the pole piece of active material that negative pole adopts the carbon material used as anode of lithium ion battery, and what wherein effect was best is hard carbon.This type of capacitor monomer specific energy has reached 20h, and the double electric layers supercapacitor specific energy of more symmetrical system is improved largely, but the difficult demand that satisfies new energy electric motor vehicle.
Lithium ion because operating voltage height, volume are little, light weight, specific energy height, memory-less effect, pollution-free, self discharge is little, have extended cycle life, be considered to the optimal energy of 21 century, the present successful fields such as mobile phone, notebook, digital camera that are applied to, but because the characteristics of lithium ion battery, under high magnification, circulate, life-span and fail safe are undesirable, to such an extent as to it is also immature in the application in new energy electric motor vehicle field.
Summary of the invention
The objective of the invention is by lithium ion is merged mutually with the design of ultracapacitor, when high power charging-discharging, ultracapacitor plays the effect of a buffer, thereby make lithium ion battery except keeping operating voltage height, advantage such as in light weight, also embody high energy density that discharges and recharges and cycle life, make high-energy-density type superbattery have broader application.
The object of the present invention is achieved like this, a kind of high-energy-density/high-specific-power type super battery, be made up of positive pole, negative pole, marginal barrier film and electrolyte, wherein, a superbattery unit is to be composed in parallel by lithium ion cell electrode and lithium ion super capacitor electrode.
Wherein, positive pole is to be formed in parallel by the electrode slice that lithium ion in the lithium ion battery embeds porous carbon materials in the electrode slice of compound-material and the ultracapacitor, negative pole adopts the lithium ion battery negative pole carbon material electrode, and electrolyte adopts the non-aqueous organic solvent electrolyte that contains lithium ion salt.
Wherein, described lithium ion embedding compound comprises: LiCoO
2, LiMn
2O
4, LiNiO
2, LiFePO
4, LiNi
0.8Co
0.2O
2, LiNi
1/3Co
1/3Mn
1/3O
2, LiMnO
2In a kind of or mixture.
Wherein, described porous carbon comprises a kind of or mixture in active carbon, carbon cloth, carbon fiber, carbon felt, carbon aerogels, the carbon nano-tube.
Wherein, described carbon material used as anode comprises that negative pole adopts the lithium ion battery negative pole carbon material electrode, comprise MCMB or, a kind of or mixture in the native graphite, Delanium, hard carbon, carbon black.
Wherein, the lithium ion in the described electrolyte is by LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2), LiBOB, LiAsF
6In at least a generation, and may add Me
3EtNBF
4, Me
2Et
2NBF
4, MeEt
3NBF
4, Et
4NBF
4, Pr
4NBF
4, MeBu
3NBF
4, Bu
4NBF
4, Hex
4NBF
4, Me
4PBF
4, Et
4PBF
4, Pr
4PBF
4, Bu
4PBF
4In one or several, the non-aqueous organic solvent in the described electrolyte comprises one or more in ethylene carbonate, propene carbonate, gamma-butyrolacton, dimethyl carbonate, diethyl carbonate, butylene, methyl ethyl carbonate, carbonic acid first propyl ester, ethylene sulfite, propylene sulfite, ethyl acetate, the acetonitrile.
Wherein, described barrier film comprises polyethene microporous membrane, microporous polypropylene membrane, polypropylene-polyethylene composite membrane, inorganic ceramic membrane, paper barrier film, nonwoven fabrics barrier film.
A kind of method for preparing high-energy-density/high-specific-power type super battery comprises:
(1) lithium ion embeds the preparation process of the positive plate of compound: lithium ion is embedded compound, conductive agent, binding agent mix, the furnishing slurry is coated on the plus plate current-collecting body then, drying, roll, cut, vacuumize is prepared into positive plate;
(2) preparation process of active carbon porous carbon materials positive plate: porous carbon materials active carbon, conductive agent, binding agent are mixed, and the furnishing slurry is coated on the plus plate current-collecting body then, drying, roll, cut, vacuumize is prepared into positive plate;
(3) preparation process of negative plate: at first lithium ion battery negative pole carbon material, conductive agent, binding agent are mixed, the furnishing slurry is coated on the negative current collector then, drying, roll, cut, vacuumize is prepared into negative plate;
(4) number of assembling steps: with the positive and negative plate for preparing through lamination or be wound into electric core, put into aluminum plastic film, aluminum hull, plastic housing or box hat, seal, be infused in the non-aqueous organic solvent electrolyte that the electrolyte that contains lithium ion in the non-aqueous organic solvent contains lithium ion salt then.
Wherein, described conductive agent comprise natural graphite powder, Delanium, carbon black, acetylene black, MCMB, hard charcoal, petroleum coke, carbon nano-tube, Graphene, in a kind of or their mixture, and described binding agent comprises in polytetrafluoroethylene, Kynoar, hydroxypropyl methylcellulose, CMC and the butadiene-styrene rubber one or more.
Wherein, the collector of described positive plate comprises aluminium foil, aluminium net, and the collector of described negative plate comprises Copper Foil, copper mesh.
High-energy-density/high-specific-power type super battery of the present invention has that to compare specific energy higher with double electric layer capacitor, compares than lithium ion battery to have the higher specific power and the advantage of cycle life preferably; Simultaneously, compare with the ultracapacitor parallel system, reduced parallel circuits between the two, increased reliability with lithium ion battery; And pole piece production is simple, and the coating apparatus of lithium ion battery is used to be coated with the positive pole and the negative pole of lithium ion battery, and the coating apparatus of ultracapacitor is used to be coated with the electric double layer positive pole, does not need to research and develop again new coating apparatus.Can be widely used in fields such as electric automobile, electric tool, solar energy storage, wind energy energy storage.
Description of drawings
Accompanying drawing 1 is high-energy-density of the present invention/high-specific-power type super battery theory structure schematic diagram.
Embodiment
Describe specific embodiments of the invention in detail below in conjunction with accompanying drawing.
As shown in Figure 1, a kind of high-energy-density/high-specific-power type super battery of the present invention, be made up of positive pole 1, negative pole 2, marginal barrier film 3 and electrolyte, wherein, a superbattery unit 8 is to be composed in parallel by lithium ion cell electrode 4 and lithium ion super capacitor electrode 5.
Wherein, anodal 1 is to be formed in parallel by the electrode slice 7 that lithium ion in the lithium ion battery embeds porous carbon materials in the electrode slice 6 of compound-material and the ultracapacitor, negative pole 2 adopts the lithium ion battery negative pole carbon material electrode, and electrolyte adopts the non-aqueous organic solvent electrolyte that contains lithium ion salt.
Among the present invention, the preparation process that lithium ion embeds the positive plate of compound is: lithium ion is embedded compound, active carbon, conductive agent, binding agent mixing, the furnishing slurry is coated on the plus plate current-collecting body then, drying, roll, cut, vacuumize is prepared into the lithium ion anode sheet; The preparation process of active carbon positive plate: with active carbon, conductive agent, binding agent mix, the furnishing slurry is coated on the plus plate current-collecting body then, drying, roll, cut, vacuumize is prepared into the active carbon positive plate, according to the degree of mixing difference, under same lithium ion cell positive, can be adopted as: after claiming that according to certain mass ratio active carbon, conductive agent, binding agent mix, be stirred to paste, be coated in then on the collector, drying, roll, cut, vacuumize is prepared into positive plate.The making step of negative plate is: take by weighing after hard carbon, binding agent mix according to certain mass ratio, be stirred to paste, be coated in then on the collector, drying, roll, cut, vacuumize is prepared into negative plate.Lithium ion described in the present invention embeds compound and comprises: LiCoO
2, LiMn
2O
4, LiNiO
2, LiFePO
4, LiNi
0.8Co
0.2O
2, LiNi
1/3Co
1/3Mn
1/3O
2Deng.Lithium ion embedding-Tuo embedding good reversibility, diffusion velocity in this class material is fast, follows the change in volume of reaction little, and they all have good cycle characteristics and large current characteristic like this.
Active carbon described in the present invention comprises the active carbon of different surface densities.
Hard carbon described in the present invention is meant difficult graphitized carbon, the characteristics that generally have specific capacity height (reaching 300-700mAh/g), good rate capability, the embedding of lithium ion in this class material simultaneously can not cause that structure significantly expands, has good charge-discharge performance, it comprises resin carbon and organic polymer RESEARCH OF PYROCARBON, described resin carbon comprises phenolic resins carbon, epoxy resin carbon, poly furfuryl alcohol resin carbon, furfural resin carbon, and described organic polymer RESEARCH OF PYROCARBON comprises benzene carbon, poly furfuryl alcohol RESEARCH OF PYROCARBON, polyvinyl chloride RESEARCH OF PYROCARBON, phenolic aldehyde RESEARCH OF PYROCARBON.Graphite described in the present invention is Palta type graphite, and its specific capacity reaches 330mAh/g, and the specific capacity of MCMB is 310mAh/g.
Lithium salts in the electrolyte described in the present invention comprises LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2), LiBOB, LiAsF
6In at least a; Non-aqueous organic solvent comprises one or more in ethylene carbonate, propene carbonate, gamma-butyrolacton, dimethyl carbonate, diethyl carbonate, butylene, methyl ethyl carbonate, carbonic acid first propyl ester, ethylene sulfite, propylene sulfite, ethyl acetate, the acetonitrile.These organic electrolytes of being made up of lithium salts have high ionic conductivity, and passage fast can be provided for the migration of lithium ion in the charge and discharge process, increase the speed of reaction; Have the characteristics such as potential range wide (being stable between 0-5V), Heat stability is good, serviceability temperature wide ranges of electrochemical stability simultaneously, the stability that makes superbattery discharge and recharge reaction improves greatly, helps the lifting of battery cycle life.
Barrier film described in the present invention comprises polyethene microporous membrane (PE), microporous polypropylene membrane (PP), composite membrane (PE+PP), inorganic ceramic membrane, paper barrier film, its thickness is generally at 10-30 μ m, the aperture has the ability and the high-temperature stability of good adsorption electrolyte at 0.03 μ m-0.05 μ m.
The collector of positive plate adopts aluminium foil, aluminium net among the present invention, and the collector of negative plate adopts Copper Foil, copper mesh.In the making of pole piece, add an amount of conductive agent and binding agent.Conductive agent adopts graphite powder, carbon black, acetylene black or their mixture with high conductivity among the present invention.Binding agent among the present invention adopts one or more in polytetrafluoroethylene (PTFE), Kynoar (PVDF), hydroxypropyl methylcellulose (HPMC), CMC (CMC) and the butadiene-styrene rubber (SBR).
Lithium ion, according to a certain percentage with active carbon, conductive agent, binding agent mixes, the furnishing slurry, be coated on the plus plate current-collecting body then, drying, roll, cut, vacuumize is prepared into the present invention of active carbon positive plate lithium ion negative pole by use the specific capacity height on negative pole, the hard carbon material that power-performance is good, (80-100wh/kg), the characteristic of high power density (4500-8000w/kg) (energy content of battery density and power density all are to calculate according to the weight of actual high-energy-density type superbattery) can be widely used in electric automobile, electric tool, solar energy storage, fields such as wind energy energy storage.
The main raw material(s) that uses among the embodiment is as follows:
LiMn
2O
4-Qingdao LNCM Co., Ltd., model is PS-10;
LiFePO
4-Tianjin Sitelan Energy Science Co., Ltd produces, and model is SLFP-ES01;
LiNi
1/3Co
1/3Mn
1/3O
2Xinxiang ,-Henan China prosperous energy and material limited company; Model is the SY-A type
Active carbon-Japanese Kuraray company produces, and model is YP-17D, and the 1# surface density is 15mg/cm
2The 2# surface density is 20mg/cm
2The 3# surface density is 25mg/cm
2
Graphite powder-Xinxiang, Henan China prosperous energy and material limited company, model is a graphite-198;
PVDF (Kynoar)-Shanghai Sanaifu New Material Co., Ltd produces, and model is FR921;
NMP (1-methyl 2-Pyrrolidone)-Jin Long chemical plant, Nanjing;
Conductive black-TIMCAL company produces, and model is Super-P;
Polyethene microporous membrane-U.S. En Taike
Embodiment 1:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiMn of 200g
2O
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 15mg/cm to be coated on the aluminium foil of 16 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the hard carbon, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiMn
2O
4Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 20g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.75V, and the specific energy of superbattery is 80Wh/Kg, specific power is 6000W/Kg, through 5A charge and discharge the circulation 2000 times after, capability retention is 85%.
Embodiment 2:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiMn of 200g
2O
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 15mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the graphite, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiMn
2O
4Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 18g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.75V, and the specific energy of superbattery is 85Wh/Kg, specific power is 5500W/Kg, through 5A charge and discharge the circulation 2000 times after, capability retention is 70%.
Embodiment 3:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiMn of 200g
2O
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the hard carbon, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiMn
2O
4Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/LLiPF
6The electrolyte 20g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.75V, and the specific energy of superbattery is 77Wh/Kg, specific power is 7000W/Kg, through 5A charge and discharge the circulation 2000 times after, capability retention is 92%.
Embodiment 4:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiMn of 200g
2O
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the 2# active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 16mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the graphite, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiMn
2O
4Anodal, 8 active carbon positive poles), barrier film, negative plate (9) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 18g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.75V, and the specific energy of superbattery is 82Wh/Kg, specific power is 6000W/Kg, through 5A charge and discharge the circulation 2000 times after, capability retention is 75%.
Embodiment 5:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiMn of 200g
2O
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the 3# active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the hard carbon, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, electric core after welding is put into the aluminum plastic film of forming, and inject 1mol/L LiPF
6The electrolyte 20g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.75V, and the specific energy of superbattery is 77Wh/Kg, specific power is 6000W/Kg, through 5A charge and discharge the circulation 2000 times after, capability retention is 94%.
Embodiment 6:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiMn of 200g
2O
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the graphite, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, just positive plate (8 LiMn
2O
4Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/LLiPF
6The electrolyte 18g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.75V, and the specific energy of superbattery is 80Wh/Kg, specific power is 5800W/Kg, through 5A charge and discharge the circulation 2000 times after, capability retention is 79%.
Table 1: adopt LiMn
2O
4Comparison with the superbattery performance of different surface density active carbons
As can be seen from the above table with LiMn
2O
4With active carbon be anodal superbattery, LiMn
2O
4Under same surface density, the specific energy of superbattery reduces along with the increase of activated carbon electrodes surface density, and specific power increases earlier and afterwards reduces, and cycle life increases.Same positive pole is that the superbattery cycle life of negative pole is better than far away with graphite with the hard carbon is the superbattery of negative pole.
Embodiment 7:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiNi of 200g
1/3Co
1/3Mn
1/3O
2, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 15mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the hard carbon, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 15g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.5V, and the specific energy of superbattery is 97Wh/Kg, specific power is 6300W/Kg, through 5A charge and discharge the circulation 10000 times after, capability retention is 92%.
Embodiment 8:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiNi of 200g
1/3Co
1/3Mn
1/3O
2, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 15mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the graphite, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 50mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 15g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.75V, and the specific energy of superbattery is 65Wh/Kg, specific power is 5600W/Kg, through 5A charge and discharge the circulation 10000 times after, capability retention is 72%.
Embodiment 9:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiNi of 200g
1/3Co
1/3Mn
1/3O
2, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the hard carbon, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 50mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 20g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.5V, and the specific energy of superbattery is 85Wh/Kg, specific power is 7500W/Kg, through 5A charge and discharge the circulation 10000 times after, capability retention is 94%.
Embodiment 10:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiNi of 200g
1/3Co
1/3Mn
1/3O
2, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the 2# active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the graphite, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 18g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.75V, and the specific energy of superbattery is 62Wh/Kg, specific power is 6000W/Kg, through 5A charge and discharge the circulation 10000 times after, capability retention is 75%.
Embodiment 11:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiNi of 200g
1/3Co
1/3Mn
1/3O
2, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the hard carbon, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 20g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.5V, and the specific energy of superbattery is 80Wh/Kg, specific power is 7300W/Kg, through 5A charge and discharge the circulation 10000 times after, capability retention is 95%.
Embodiment 12:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiNi of 200g
1/3Co
1/3Mn
1/3O
2, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the graphite, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 15g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 4.2V, leave standstill 5min, 5A is discharged to 2.75V, and the specific energy of superbattery is 90Wh/Kg, specific power is 7300W/Kg, through 5A charge and discharge the circulation 10000 times after, capability retention is 78%.
Table 2: adopt LiNi
1/3Co
1/3Mn
1/3O
2Comparison with the superbattery performance of different activities charcoal
As can be seen from the above table with LiNi
1/3Co
1/3Mn
1/3O
2With active carbon be anodal superbattery, LiMn
2O
4Under same surface density, the specific energy of superbattery reduces along with the increase of activated carbon electrodes surface density, and specific power increases earlier and afterwards reduces, and cycle life increases.Same positive pole is that the superbattery cycle life of negative pole is better than far away with graphite with the hard carbon is the superbattery of negative pole.
Embodiment 13:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiFePO of 200g
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 15mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the hard carbon, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (9) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 20g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 3.7V, leave standstill 5min, 5A is discharged to 2.5V, and the specific energy of superbattery is 60Wh/Kg, specific power is 6000W/Kg, through 5A charge and discharge the circulation 20000 times after, capability retention is 90%.
Embodiment 14:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiFePO of 200g
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the 1# active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 15mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the graphite, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 45mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (9) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 18g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 3.7V, leave standstill 5min, 5A is discharged to 2.5V, and the specific energy of superbattery is 70Wh/Kg, specific power is 5400W/Kg, through 5A charge and discharge the circulation 20000 times after, capability retention is 70%.
Embodiment 15:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiFePO of 200g
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the hard carbon, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 20g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 3.7V, leave standstill 5min, 5A is discharged to 2.5V, and the specific energy of superbattery is 60Wh/Kg, specific power is 6500W/Kg, through 5A charge and discharge the circulation 20000 times after, capability retention is 92%.
Embodiment 16:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiFePO of 200g
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 20mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the graphite, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 18g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 3.7V, leave standstill 5min, 5A is discharged to 2.5V, and the specific energy of superbattery is 68Wh/Kg, specific power is 5900W/Kg, through 5A charge and discharge the circulation 20000 times after, capability retention is 75%.
Embodiment 17:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiFePO of 200g
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the hard carbon, PVDF that with total amount are 400g are to mix at 92: 8 by the matter anharmonic ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, with positive plate (8 LiNi
1/3Co
1/3Mn
1/3O
2Anodal, 8 active carbon positive poles), barrier film, negative plate (17) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, and the electric core after welding is put into the aluminum plastic film of forming, and injects 1mol/L LiPF
6The electrolyte 20g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 3.7V, leave standstill 5min, 5A is discharged to 2.5V, and the specific energy of superbattery is 55Wh/Kg, specific power is 6400W/Kg, through 5A charge and discharge the circulation 20000 times after, capability retention is 93%.
Embodiment 18:
Lithium ion embeds the preparation process of the positive plate of compound: with total amount is the LiFePO of 200g
4, conductive black, PVDF be to mix at 85: 8: 7 by mass ratio, with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The preparation process of active carbon positive plate is: the 3# active carbon, conductive black, PVDF that with total amount are 200g are to mix at 90: 5: 5 by mass ratio, and with NMP furnishing slurry, (the coating weightening finish is: 25mg/cm to be coated on the aluminium foil of 20 μ m then
2) on, drying (110～120 ℃), roll, cut-parts (are of a size of: 37*59mm
2), 24h vacuumize (120～130 ℃) is made into positive plate; The making of negative plate: the graphite, PVDF that with total amount are 400g are to mix at 92: 8 by mass ratio, with NMP furnishing slurry, are coated on then that (the coating weightening finish is: 20mg/cm on the Copper Foil of 16 μ
2), drying (110～120 ℃), roll, cut-parts (are of a size of: 38*60mm
2), 24h vacuumize (120～130 ℃) is made into negative plate.Selecting polyethene microporous membrane for use is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into electric core, the anodal utmost point group of the electric core that will fold is welded on the aluminum lug then, negative pole utmost point group is welded on the nickel system lug, electric core after welding is put into the aluminum plastic film of forming, and inject 1mol/L LiPF
6The electrolyte 18g of-EC (ethylene carbonate)/DEC (diethyl carbonate) (1: 1) is assembled into the square superbattery.Superbattery carries out performance test after changing into, the test system is that 5A charges to 3.7V, leave standstill 5min, 5A is discharged to 2.5V, and the specific energy of superbattery is 65Wh/Kg, specific power is 6400W/Kg, through 5A charge and discharge the circulation 20000 times after, capability retention is 80%.
Table 3: adopt LiFePO
4Comparison with the superbattery performance of different activities charcoal
As can be seen from the above table with LiFePO
4With active carbon be anodal superbattery, LiMn
2O
4Under same surface density, the specific energy of superbattery reduces along with the increase of activated carbon electrodes surface density, and specific power increases earlier and afterwards reduces, and cycle life increases.Same positive pole is that the superbattery cycle life of negative pole is better than far away with graphite with the hard carbon is the superbattery of negative pole.
Described in this specification is several preferred embodiment of the present invention, and above embodiment is only in order to illustrate technical scheme of the present invention but not limitation of the present invention.All those skilled in the art all should be within the scope of the present invention under this invention's idea by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. a high-energy-density/high-specific-power type super battery is made up of positive pole, negative pole, marginal barrier film and electrolyte, it is characterized in that a superbattery unit is to be composed in parallel by lithium ion cell electrode and lithium ion super capacitor electrode.
2. high-energy-density/high-specific-power type super battery according to claim 1, it is characterized in that positive pole is to be formed in parallel by the electrode slice that lithium ion in the lithium ion battery embeds porous carbon materials in the electrode slice of compound-material and the ultracapacitor, negative pole adopts the lithium ion battery negative pole carbon material electrode, and electrolyte adopts the non-aqueous organic solvent electrolyte that contains lithium ion salt.
3. high-energy-density/high-specific-power type super battery according to claim 1 is characterized in that described lithium ion embeds compound and comprises: LiCoO
2, LiMn
2O
4, LiNiO
2, LiFePO
4, LiNi
0.8Co
0.2O
2, LiNi
1/3Co
1/3Mn
1/3O
2, LiMnO
2In a kind of or mixture.
4. high-energy-density according to claim 1/high-specific-power type super battery superbattery is characterized in that described porous carbon comprises a kind of or mixture in active carbon, carbon cloth, carbon fiber, carbon felt, carbon aerogels, the carbon nano-tube.
5. according to the described high-energy-density/high-specific-power type super battery of claim 1 superbattery, it is characterized in that described carbon material used as anode comprises that negative pole adopts the lithium ion battery negative pole carbon material electrode, comprise MCMB or, a kind of or mixture in the native graphite, Delanium, hard carbon, carbon black.
6. high-energy-density/high-specific-power type super battery according to claim 1 is characterized in that lithium ion in the described electrolyte is by LiClO
4, LiBF
4, LiPF
6, LiCF
3SO
3, LiN (CF
3SO
2), LiBOB, LiAsF
6In at least a generation, and may add Me
3EtNBF
4, Me
2Et
2NBF
4, MeEt
3NBF
4, Et
4NBF
4, Pr
4NBF
4, MeBu
3NBF
4, Bu
4NBF
4, Hex
4NBF
4, Me
4PBF
4, Et
4PBF
4, Pr
4PBF
4, Bu
4PBF
4In one or several, the non-aqueous organic solvent in the described electrolyte comprises one or more in ethylene carbonate, propene carbonate, gamma-butyrolacton, dimethyl carbonate, diethyl carbonate, butylene, methyl ethyl carbonate, carbonic acid first lactone, ethylene sulfite, propylene sulfite, ethyl acetate, the acetonitrile.
7. high-energy-density according to claim 1/high-specific-power type super battery superbattery is characterized in that described barrier film comprises polyethene microporous membrane, microporous polypropylene membrane, polypropylene-polyethylene composite membrane, inorganic ceramic membrane, paper barrier film, nonwoven fabrics barrier film.
8. method for preparing high-energy-density/high-specific-power type super battery according to claim 1 comprises:
(1) lithium ion embeds the preparation process of the positive plate of compound: lithium ion is embedded compound, conductive agent, binding agent mix, the furnishing slurry is coated on the plus plate current-collecting body then, drying, roll, cut, vacuumize is prepared into positive plate;
(2) preparation process of active carbon porous carbon materials positive plate: porous carbon materials active carbon, conductive agent, binding agent are mixed, and the furnishing slurry is coated on the plus plate current-collecting body then, drying, roll, cut, vacuumize is prepared into positive plate;
(3) preparation process of negative plate: at first lithium ion battery negative pole carbon material, conductive agent, binding agent are mixed, the furnishing slurry is coated on the negative current collector then, drying, roll, cut, vacuumize is prepared into negative plate;
(4) number of assembling steps: with the positive and negative plate for preparing through lamination or be wound into electric core, put into aluminum plastic film, aluminum hull, plastic housing or box hat, seal, be infused in the non-aqueous organic solvent electrolyte that the electrolyte that contains lithium ion in the non-aqueous organic solvent contains lithium ion salt then.
9. method according to claim 8, wherein said conductive agent comprise natural graphite powder, Delanium, carbon black, acetylene black, MCMB, hard charcoal, petroleum coke, carbon nano-tube, Graphene, in a kind of or their mixture, and described binding agent comprises in polytetrafluoroethylene, Kynoar, hydroxypropyl methylcellulose, CMC and the butadiene-styrene rubber one or more.
10. method according to claim 8, the collector of wherein said positive plate comprise aluminium foil, aluminium net, and the collector of described negative plate comprises Copper Foil, copper mesh.
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