CN103311501B - Cell positive material and preparation method thereof and made super capacitance cell - Google Patents
Cell positive material and preparation method thereof and made super capacitance cell Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 11
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 57
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 41
- 239000003792 electrolyte Substances 0.000 claims description 33
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 24
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 14
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910014169 LiMn2-xMxO4 Inorganic materials 0.000 description 1
- 229910014435 LiMn2−xMxO4 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RTFUSLIFSOPNOT-UHFFFAOYSA-K [O-]P([O-])([O-])=O.[Li+].O.[V+5] Chemical compound [O-]P([O-])([O-])=O.[Li+].O.[V+5] RTFUSLIFSOPNOT-UHFFFAOYSA-K 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of cell positive material and preparation method thereof and made super capacitance cell, belong to electrochemical energy storing device field. Technical problem solved by the invention is to provide a kind of lithium ion battery and ultracapacitor battery of advantage separately of combining. Cell positive material of the present invention is composited by weight 1:2.36～5.91 by super-activated carbon and lithium phosphate; Super capacitance cell of the present invention, its positive electrode is to be composited by weight 1:2.36～5.91 by super-activated carbon and lithium phosphate, super capacitance cell of the present invention can be in 10 minutes between 0.0～7.0V fast charging and discharging, the trend that discharges and recharges, between lithium ion battery and ultracapacitor, has a charge and discharge platform in 2.8V left and right; Specific energy is about 190Wh/kg, exceedes the level of lithium ion battery; Specific power is about 1.6kW/kg, and after high rate cyclic 2,000 times, capability retention is greater than 80%.
Description
Technical field
The present invention relates to a kind of cell positive material and preparation method thereof, and adopt this kind of positive electrodeThe super capacitance cell of making, belongs to electrochemical energy storing device field.
Background technology
As efficient rechargeable battery, lithium ion battery has been widely used in various portable electronics and has producedOn product and electric tool. Lithium ion battery generally adopts cobalt acid lithium (LiCoO at present2) as anodalMaterial, graphite material or MCMB material be as negative material, lithium hexafluoro phosphate (LiPF6）Be dissolved in the solution of carbonic ester as electrolyte. In the time that lithium ion battery is discharged and recharged, on positive and negative electrode allCan there is electrochemical reaction; Therefore can think, identical with other common batteries, lithium ion battery isStore and release energy by electrochemical reaction, also thering is electrochemical energy storage mechanism.
Ultracapacitor is also a kind of rechargeable battery. The general principle of ultracapacitor and ordinary capacitorIdentical with structure, be all to be formed by positive pole, negative pole and electrolyte three parts. The difference of the two is,The specific area of ultracapacitor electrode used therein is much larger than ordinary capacitor. Business-like super electricity at presentContainers electrode material is generally super-activated carbon, and specific area is greater than 2000m2/ g. When outside useWhen power supply charges to capacitor, positive electrode surface will progressively accumulate positive charge, and negative material surfaceTo progressively accumulate negative electrical charge; Meanwhile, be subject to the effect of the electrostatic attraction of electric charge on electrode, in electrolyteAnion will be adsorbed on positive electrode surface, and cation will be adsorbed on negative material surface; Institute inhalesElectric charge equal and opposite in direction on electric charge and the electrode of attached ion, but symbol is contrary, forms electric double layer; SolutionRemain electroneutral. When disconnecting after external power, the electric charge in electrode material can continue stable existence.Mechanism according to this, capacitor can store electric charge and corresponding energy by electric double layer mechanism. When electric dischargeProcess is contrary with when charging, and the electric charge storing on electrode will neutralize after overload (external resistance),With stored energy, load is done work simultaneously; The ion of electrode surface absorption also comes back to solutionIn. Can find out, ultracapacitor is to carry out storage power by electric double layer mechanism.
According to above-mentioned electric double layer mechanism, ultracapacitor can discharge stored energy with the form of electric energy,Therefore also can be regarded as a kind of battery from the angle of application; Ultracapacitor and common batteries the twoAlso similar in structure, be all to be formed by positive pole, negative pole and electrolyte three parts; But the two is in principleHave essential distinction: common batteries be the electrochemical reaction by relating to intermolecular electron exchange store andRelease energy, but ultracapacitor is by simple charge storage and release in electric double layer, comesRealize storage and the release of energy. Also can be understood as, common batteries is to store up in the mode of chemical energyDeposit energy, in the time of electric discharge, chemical energy is converted into electric energy, and then externally acting; And ultracapacitorBe to carry out storage power in the mode of electric energy, in the time of electric discharge, directly externally do work with stored electric energy; CauseThis, from the angle of power conversion, the electric double layer mechanism of ultracapacitor is than the electrification of common batteriesMechanism is simply too much, there is no the conversion links between electric energy and chemical energy. Due to ultracapacitorOnly there is solution resistance in inside in the time discharging and recharging, and common batteries also exists electrochemistry anti-in the time discharging and rechargingThe impedance of answering, therefore the internal resistance of ultracapacitor is much smaller than common batteries; This feature is conducive to superThe high current charge-discharge of capacitor. General existence discharge platform, for example lithium when common batteries electric dischargeThe discharge voltage plateau of ion battery is about 3.7V, and this is to be determined by the electrochemical reaction of being correlated with;But the discharge voltage of ultracapacitor is linear decline with discharge time, do not have discharge voltage plateau,This is to be determined by the characteristic of capacitor.
When to common ultracapacitor charging, the anion in electrolyte will be adsorbed onto anodal livingProperty Carbon Materials surface, simultaneously the cation in electrolyte will be adsorbed onto the table of cathode activated charcoalFace; Obviously, this process will reduce the ion concentration in electrolyte, and reduces electrolyteIonic conductivity. In the time that the charging voltage of ultracapacitor reaches certain value, in electrolyte fromSon will be exhausted, is all adsorbed to the surface of both positive and negative polarity; This has just limited ultracapacitorMaximum charging voltage.
As two kinds of different rechargeable batteries, lithium ion battery and ultracapacitor respectively have superiority and defect.The specific energy of lithium ion battery is high, is about 170Wh/kg; Discharging voltage balance, discharge voltage is about3.7V; But specific power is low, be about 0.7kW/kg; Cycle life is shorter, is about 500 times. SuperThe specific power of capacitor is large, is about 4kW/kg; Have extended cycle life, be about 100,000 times; But specific energyLow, be about 5Wh/kg; Discharge off platform.
Existing a lot of patented invention imaginations combine lithium ion battery and ultracapacitor, design onePlant between the rechargeable battery between the two, namely allow an electrode picture of battery in lithium ion batteryWork like that, store and release energy by electrochemical reaction; And allow another electrode picture superIn capacitor, work like that, store and release energy by electric double layer mechanism. In document generally by thisPlant battery and be called hybrid super capacitor or asymmetric super-capacitor. Here by this novel fillingElectricity battery is called " super capacitance cell ", also with the battery of ultracapacitor character.
About the domestic patent of invention of super capacitance cell is a lot, roughly can be divided into water system and organic systemTwo large classes, adopt respectively aqueous electrolyte and organic solution electrolyte; Wherein the latter's charging voltageWill be higher than the former. According to electromagnetic theory, the energy E of capacitor stores and charging voltage V's is flat(E=0.5CV is just directly proportional2), and only with more linear than capacitor C; Obviously, improve charged electricalPressure ratio is carried high specific capacitance can more effectively improve the super specific energy that holds battery.
8 examples about the domestic patent of invention of ultracapacitor or super capacitance cell:
Patent 1: the patent No. is CN200910219706.6, patent name is " a kind of hybrid super electricityContainer ". The positive pole of this invention adopts the lithium-containing compounds such as vanadium phosphate oxygen lithium, and negative pole adopts lithium titanate etc.Lithium-containing compound, organic electrolyte is made up of the electrolytic salt that contains lithium ion and mixed organic solvents.It is said, this super battery that holds has higher specific energy. The positive and negative electrode material in fact, here is all seenNot going out to have electric double layer energy storage mechanism, can not regard a kind of super capacitance cell as, is only a kind of commonLithium ion battery.
Patent 2: the patent No. is CN200810200714.1, patent name is " organic mixed superCapacitor ". The positive pole of this invention adopts lithium ion to embed compound, for example LiCoO2、LiMn2O4、LiNiO2、LiFePO4Deng; Negative pole adopts the mixture of hard carbon and porous carbon materials; Electrolyte adoptsThe organic solution that contains lithium ion. The specific energy of this super capacitance cell can reach 45～80Wh/kg,Specific power > 4500W/kg.
Patent 3: the patent No. is CN200910037614.6, patent name is " a kind of hybrid electrochemicalCapacitor ". It is lithium intercalation compound and active carbon that the positive pole of this invention adopts iron system, vanadium system or nickel manganese cobaltMixture or compound; Negative pole adopts absorbent charcoal material; Electrolyte employing contains supporting electrolyteLithium salt solution, can be water system, can be also organic system. This super capacitance cell has improved greatly greatlyMultiplying power discharging property. But its specific capacity is low.
Patent 4: the patent No. is CN200610109423.2, patent name is " organic electrolyte systemHybrid electrochemical capacitor and preparation method thereof ". The positive pole of this invention adopts ion insert material; NegativeThe utmost point adopts porous carbon materials; Electrolyte adopts organic electrolyte solution. The specific energy of this super capacitance cellAmount is 8Wh/kg, and specific power is 2～3W/kg.
Patent 5: the patent No. is CN200510110461.5, patent name is " lithium ion battery materialAs anodal non-aqueous system electrochemical mixed capacitor ". The positive pole of this invention adopts the high current potential that embedsLithium ion embed compound-material LiMn2-xMxO4Material; Negative pole adopts super-activated carbon. ThoughSo its cycle life and high rate performance are better than lithium ion battery, and specific energy can reach the number of double layer capacitorDoubly. But the specific energy of this mixed capacitor does not still reach the specific energy of lithium battery, and electrical conductivityLower.
Patent 6: the patent No. is CN201210438987.6, patent name is " a kind of lithium ion superCapacitor ". The positive pole of this invention adopts porous carbon materials and LiNixCoyMnzO2, its porous carbonMaterial is at least one in active carbon or active charcoal fiber or porous, electrically conductive carbon black or Graphene; Negative poleAdopt graphite type material; Electrolyte is made up of electrolytic salt and organic solvent, described electrolytic salt choosingFrom LiPF6、LiBF4, LiBOB or LiFSi; Described organic solvent is ethylene carbonate or carbonic acidAt least one in propylene, ethylene methyl esters, dimethyl carbonate, diethyl carbonate or acetonitrile. ShouldThe specific energy of super capacitance cell can reach about 150Wh/kg.
Patent 7: the patent No. is CN200710011992.8, patent name is " a kind of lithium ion superCapacitor and assemble method thereof ". The positive pole of this invention adopts the active carbon with electric double layer energy storage mechanismMaterial; Negative pole adopts amorphous titanium oxide nanotube or the nanostructured with lithium-ion energy storage mechanism; ElectricitySeparating liquid is made up of lithium salts and organic solvent. Because the electron conduction of lithium titanate class negative material is too low,Be unfavorable for the heavy-current discharge of battery, can limit the specific power of battery; The specific energy of this super capacitance cellAmount is 100Wh/kg, and specific power is 30kW/kg.
Patent 8: the patent No. is CN200410084316.X, and patent name is for " to use lithium ion battery batteryThe electrochemical super-capacitor of utmost point material as cathode ". The positive pole of this invention adopts the active carbon of high-ratio surfaceOr mesoporous carbon; Negative pole adopts the lithium ion with low embedding current potential to embed compound, specifically adopts nanometerThe Li of spinel-type8x/(x+4)Ti8/(x+4)O4Or the compound of monobasic or polynary other doped with metal elements;Electrolyte adopts organic electrolyte solution. . Because the electron conduction of lithium titanate class negative material is too low,Be unfavorable for the heavy-current discharge of battery, can limit the specific power of battery; Although cycle life is longer than lithiumIon battery, but its specific energy is not high, only can reach the three to four-fold of double layer capacitor.
Summary of the invention
The technical problem that the present invention mainly solves be to provide a kind of cell positive material and preparation method thereof andMade super capacitance cell.
Cell positive material of the present invention, by super-activated carbon and lithium phosphate 1:2.36～5.91 by weightBe composited, wherein, described super-activated carbon is specific area >=2000m2The active carbon of/g.
Prepare the method for cell positive material of the present invention, comprise the steps: phosphoric acid solution and superActive carbon mixes; Then add lithium hydroxide solution, isolated by filtration; Be precipitated, will precipitate oven dry,After pulverizing, obtain cell positive material.
Further, preferably super-activated carbon and pure phosphoric acid are 1:2～5 by weight.
Further, the mass percentage concentration of preferably phosphoric acid solution is 5～50%, and more preferably phosphoric acid is moltenThe mass percentage concentration of liquid is 10～30%.
Further, owing to being subject to the solubility limit of lithium hydroxide, the biggest quality hundred of lithium hydroxidePoint concentration is 11.3%, and preferably the mass percentage concentration of lithium hydroxide solution is 5～11%, more preferablyThe mass percentage concentration of lithium hydroxide solution is 9.5%.
Because lithium hydroxide and phosphatase reaction generate lithium phosphate, so preferred rubbing of lithium hydroxide and phosphoric acidYou are than being 3:1.
In order to reach better drying effect, the temperature of drying in the preparation process of preferred battery positive electrodeDegree is 150～200 DEG C.
In order to make follow-up making anode better effects if, in the preparation process of preferred battery positive electrodeThe particle diameter of pulverizing is 25～35 μ m.
Super capacitance cell of the present invention, anode adopts described being pressed by super-activated carbon and lithium phosphateThe cell positive material that weight ratio 1:2.36～5.91 are composited.
Further, preferably super capacitance cell negative electrode adopts graphite type material.
Further, preferred described graphite type material comprises native graphite, Delanium and composite stoneOne or more in China ink.
Further, because the decomposition voltage of electrolyte is high, the charging voltage of battery just can be high, electricityThe specific capacity in pond just can be high, so the electrolyte of preferred described super capacitance cell is for having decomposition voltageBe greater than the lithium-ion battery electrolytes of 7.0V.
The production method of described super capacitance cell, after described positive electrode and battery binding agent are mixed,Be coated on aluminium foil surface, coating layer thickness is about 150～200 μ m, dries and obtains anode; By electricityPositive pole, negative pole, electrolyte and the battery miscellaneous part in pond are assembled, and obtain of the present invention superCapacitor batteries.
Battery binding agent is to make the conventional binding agent of battery. For example: PVA (polyvinyl alcohol), poly-fourPVF, sodium carboxymethylcellulose, TPO, (PVDF/NMP) or other dicyandiamide solutions, stickyTie well behaved SBR rubber, Viton, polyurethane etc.
The operation principle of super capacitance cell of the present invention:
When to super capacitance cell charging of the present invention, on the absorbent charcoal material in positive pole, just will accumulateElectric charge, forms carbonium ion (C on surface+), the lithium ion (Li in the lithium phosphate of adsorption simultaneously+）To be subject to the electrostatic repulsion of carbonium ion and deviate from from positive pole, entering into electrolyte, stayingPhosphate anion (PO4 3-) will form electric double layer, positive pole with together with the carbonium ion of activated carbon surfaceMaterial still keeps electroneutral on the whole; Meanwhile, with lithium ion battery in the situation phase of negative poleWith, the lithium ion in solution will be embedded in the interlayer structure of graphite type material. When to battery discharge,Said process reverses. Can find out, while discharging and recharging, here the desorption of the anodal upper lithium ion occurring orAdsorption process only relates to the electrostatic interaction between electric charge, has electric double layer energy storage mechanism; And negative poleThe embedding of the lithium ion of upper generation or to deviate from process be but electrochemical reaction, reaction equation is (Li++6C+e-←→LiC6), there is electrochemical energy storage mechanism. Therefore,, for energy storage mechanism, see this from positive poleIn be a ultracapacitor, and see it is a lithium ion battery here from negative pole. Whole battery is realOn border, being a battery with ultracapacitor character, is also super capacitance cell.
In super capacitance cell of the present invention, in composite super-activated carbon act as form twoElectricity layer provides great specific area; Make battery there is high capacitance. Lithium phosphate is that positive pole is carriedFor forming electric double layer required anion, simultaneously for negative pole provide the lithium that inserts graphite crystal fromSon.
The present invention adopts graphite negative electrodes material, is mainly the circulation that utilizes graphite negative electrodes materialLife-span is long, and specific capacity is high, and the advantage such as ion diffusion velocity is fast. For lithium ion battery,The cycle life of graphite negative electrodes material approximately 2,000 times, the about 340mAh/g of specific capacity and lithium ion expandLoose speed is far above the various positive electrodes of lithium ion battery.
The beneficial effect that the present invention has:
1, in the present invention, adopt the active carbon of high-specific surface area to form cell positive material, make the present invention superLevel capacitor batteries has high capacitance.
2, the present invention adopts graphite type material as negative material, makes super capacitance cell tool of the present inventionHave have extended cycle life, specific capacity is high, lithium ion diffusion velocity is fast advantage.
3, the positive pole of Novel super capacitor batteries of the present invention adopts the composite wood of active carbon and lithium phosphateMaterial. When to this super capacitance cell charging, be no longer that the Anion-adsorption in electrolyte just arrivesUtmost point activated carbon surface, but lithium ion in positive pole deviates from and enters into electrolyte, leaves phosphorusAcid ion is also adsorbed on activated carbon surface, and the lithium ion in electrolyte will be embedded into stone simultaneouslyIn China ink class negative material; Such mechanism does not change the ion concentration in electrolyte; FromAnd make super capacitance cell of the present invention there is higher charging voltage.
4, super capacitance cell of the present invention just has an electric double layer energy storage mechanism, and negative pole has electrificationLearn energy storage mechanism, actual is a kind of super capacitor electricity between lithium ion battery and ultracapacitorPond, it combines lithium ion battery and ultracapacitor advantage separately; Overcome lithium battery specific powerLow, be approximately 0.7kW/kg and ultracapacitor specific energy is low, be approximately 5Wh/kg, discharge off is flatThe shortcoming of platform. This super capacitance cell can charge and discharge fast in 10 minutes between 0.0～7.0VElectricity, the trend that discharges and recharges, between lithium ion battery and ultracapacitor, has one in 2.8V left and rightCharge and discharge platform; Specific energy is about 190Wh/kg, exceedes the level of lithium ion battery; Specific power approximatelyFor 1.6kW/kg, after high rate cyclic 2,000 times, capability retention is greater than 80%.
Brief description of the drawings
Fig. 1 is the 10th charging and discharging curve of the super capacitance cell prepared of the embodiment of the present invention 1;
Detailed description of the invention
Cell positive material of the present invention, by super-activated carbon and lithium phosphate 1:2.36～5.91 by weightBe composited, wherein, described super-activated carbon is specific area >=2000m2The active carbon of/g.
Prepare the method for cell positive material of the present invention, comprise the steps: phosphoric acid solution and superActive carbon mixes; Then add lithium hydroxide solution, isolated by filtration; Be precipitated, will precipitate oven dry,After pulverizing, obtain cell positive material.
Further, preferably super-activated carbon and pure phosphoric acid are 1:2～5 by weight.
Further, the mass percentage concentration of preferably phosphoric acid solution is 5～50%, and more preferably phosphoric acid is moltenThe mass percentage concentration of liquid is 10～30%.
Further, owing to being subject to the solubility limit of lithium hydroxide, the biggest quality hundred of lithium hydroxidePoint concentration is 11.3%, and preferably the mass percentage concentration of lithium hydroxide solution is 5～11%, more preferablyThe mass percentage concentration of lithium hydroxide solution is 9.5%.
Because lithium hydroxide and phosphatase reaction generate lithium phosphate, so preferred rubbing of lithium hydroxide and phosphoric acidYou are than being 3:1.
In order to reach better drying effect, the temperature of drying in the preparation process of preferred battery positive electrodeDegree is 150～200 DEG C.
In order to make follow-up making anode better effects if, in the preparation process of preferred battery positive electrodeThe particle diameter of pulverizing is 25～35 μ m.
Super capacitance cell of the present invention, anode adopts described being pressed by super-activated carbon and lithium phosphateThe cell positive material that weight ratio 1:2.36～5.91 are composited.
Further, preferably super capacitance cell negative electrode adopts graphite type material.
Further, preferred described graphite type material comprises native graphite, Delanium and composite stoneOne or more in China ink.
Further, because the decomposition voltage of electrolyte is high, the charging voltage of battery just can be high, electricityThe specific capacity in pond just can be high, so the electrolyte of preferred described super capacitance cell is for having decomposition voltageBe greater than the lithium-ion battery electrolytes of 7.0V.
The production method of described super capacitance cell, after described positive electrode and battery binding agent are mixed,Be coated on aluminium foil surface, coating layer thickness is about 150～200 μ m, dries and obtains anode; By electricityPositive pole, negative pole, electrolyte and the battery miscellaneous part in pond are assembled, and obtain of the present invention superCapacitor batteries.
Battery binding agent is to make the conventional binding agent of battery. For example: PVA (polyvinyl alcohol), poly-fourPVF, sodium carboxymethylcellulose, TPO, (PVDF/NMP) or other dicyandiamide solutions, stickyTie well behaved SBR rubber, Viton, polyurethane etc.
The operation principle of super capacitance cell of the present invention:
When to super capacitance cell charging of the present invention, on the absorbent charcoal material in positive pole, just will accumulateElectric charge, forms carbonium ion (C on surface+), the lithium ion (Li in the lithium phosphate of adsorption simultaneously+）To be subject to the electrostatic repulsion of carbonium ion and deviate from from positive pole, entering into electrolyte, stayingPhosphate anion (PO4 3-) will form electric double layer, positive pole with together with the carbonium ion of activated carbon surfaceMaterial still keeps electroneutral on the whole; Meanwhile, with lithium ion battery in the situation phase of negative poleWith, the lithium ion in solution will be embedded in the interlayer structure of graphite type material. When to battery discharge,Said process reverses. Can find out, while discharging and recharging, here the desorption of the anodal upper lithium ion occurring orAdsorption process only relates to the electrostatic interaction between electric charge, has electric double layer energy storage mechanism; And negative poleThe embedding of the lithium ion of upper generation or to deviate from process be but electrochemical reaction, reaction equation is (Li++6C+e-←→LiC6), there is electrochemical energy storage mechanism. Therefore,, for energy storage mechanism, see this from positive poleIn be a ultracapacitor, and see it is a lithium ion battery here from negative pole. Whole battery is realOn border, being a battery with ultracapacitor character, is also super capacitance cell.
In super capacitance cell of the present invention, in composite super-activated carbon act as form twoElectricity layer provides great specific area; Make battery there is high capacitance. Lithium phosphate is that positive pole is carriedFor forming electric double layer required anion, simultaneously for negative pole provide the lithium that inserts graphite crystal fromSon.
The present invention adopts graphite negative electrodes material, is mainly the circulation that utilizes graphite negative electrodes materialLife-span is long, and specific capacity is high, and the advantage such as ion diffusion velocity is fast. For lithium ion battery,The cycle life of graphite negative electrodes material approximately 2,000 times, the about 340mAh/g of specific capacity and lithium ion expandLoose speed is far above various positive electrodes.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, not thereforeLimit the present invention among described scope of embodiments.
The preparation of embodiment 1 super capacitance cell
Get 1kg mono-hydronium(ion) oxidation lithium, be dissolved in about 5kg deionized water; Get 0.916kg commercially available85% phosphoric acid, adds the dilution of 4kg deionized water; In this phosphoric acid,diluted, add 0.389kg super-activeCharcoal, stirs 2 hours, allows phosphoric acid solution fully infiltrate active carbon; Under agitation, in system, addSlowly lithium hydroxide solution; Isolated by filtration, is precipitated, and will be deposited at 150 DEG C and dry; EnduringCrushing material after dry, to approximately 30 μ m, obtains cell positive material. According to conventionally preparing lithium-ion electricThe technique in pond, is dissolved in the binding agent of preparing in 1-METHYLPYRROLIDONE, this just with KynoarUtmost point material is coated on aluminium foil, and dries, and obtains the positive electrode of moulding, controls coating layer thickness and is about200 μ m. According to the technique of conventionally preparing lithium ion battery, apply the positive electrode of this moulding, with formerThe electrolyte that have lithium ion battery graphite negative electrodes material, there is high de-agglomeration voltage together with barrier film,Be assembled into 18650 type batteries. Between 0.0～7.0V 20A constant current charge-discharge, measures this batteryChemical property. The 10th charging and discharging curve of super capacitance cell prepared by embodiment 1 is as Fig. 1Shown in.
The preparation of embodiment 2 super capacitance cells
Get 1kg mono-hydronium(ion) oxidation lithium, be dissolved in about 5kg deionized water; Get 0.916kg commercially available85% phosphoric acid, adds the dilution of 3kg deionized water; In this phosphoric acid,diluted, add 0.259kg super-activeCharcoal, stirs 1.5 hours, allows phosphoric acid solution fully infiltrate active carbon. Under agitation, in system, delaySlowly add lithium hydroxide solution, the mol ratio of controlling lithium hydroxide and phosphoric acid is 3:1; Isolated by filtration,Be precipitated, will be deposited at 175 DEG C and dry. Crushing material after boiling dry is arrived to approximately 30 μ m left and right,Obtain cell positive material. According to the technique of conventionally preparing lithium ion battery, be dissolved in KynoarThe binding agent of preparing in 1-METHYLPYRROLIDONE, is coated on this positive electrode on aluminium foil, and dries,Obtain the positive electrode of moulding, control coating layer thickness and be about 175 μ m. According to conventionally preparing lithium ionThe technique of battery, applies the positive electrode of this moulding, with original lithium ion battery graphite negative electrodes materialMaterial, together with having the electrolyte of high de-agglomeration voltage, is assembled into 18650 type batteries. 0.0～7.0V itBetween 20A constant current charge-discharge, measure the chemical property of this battery.
The preparation of embodiment 3 super capacitance cells
Get 1kg mono-hydronium(ion) oxidation lithium, be dissolved in about 5kg deionized water; Get 0.916kg commercially available85% phosphoric acid, adds the dilution of 2kg deionized water; In this phosphoric acid,diluted, add 0.195kg super-activeCharcoal; Stir 1 hour, allow phosphoric acid solution fully infiltrate active carbon. Under agitation, in system slowlyAdd lithium hydroxide solution; Isolated by filtration, heating, drying at 200 DEG C; The material powder after boiling dryBroken to approximately 30 μ m left and right, obtain cell positive material; According to the technique of conventionally preparing lithium ion battery,Be dissolved in the binding agent of preparing in 1-METHYLPYRROLIDONE with Kynoar, this positive electrode coatingOn aluminium foil, and dry, obtain the positive electrode of moulding, control coating layer thickness and be about 150 μ m;According to the technique of conventionally preparing lithium ion battery, apply the positive electrode of this moulding, with original lithium ionBattery together with having the electrolyte of high de-agglomeration voltage, is assembled into 18650 with graphite negative electrodes materialType battery; 20A constant current charge-discharge between 0.0～7.0V, measures the chemical property of this battery.
The chemical property of the super capacitance cell of the present invention that table 1 makes for above-described embodiment.
Table 1 super capacitance cell chemical property parameter
Note: specific energy, charging interval and the specific power in table all refers to the mensuration of the 10th circulation timeValue, capability retention refers to initial divided by circulation time first of the solid measure value of circulation after 2,000 timesValue.
Claims (7)
1. cell positive material, is characterized in that: by super-activated carbon and lithium phosphate by weight1:2.36～5.91 are composited, and wherein, described super-activated carbon is specific area >=2000m2/gActive carbon; Described positive electrode is prepared in the following ways, by mixed to phosphoric acid solution and super-activated carbonEven; Then add lithium hydroxide solution, isolated by filtration; Be precipitated, will precipitate oven dry, after pulverizingObtain cell positive material, wherein super-activated carbon and pure phosphoric acid are 1:2～5 by weight, phosphoric acidThe mass percentage concentration of solution is 5～50%, the mass percentage concentration of lithium hydroxide solution is 5～11%, the mol ratio of lithium hydroxide and phosphoric acid is 3:1, and the temperature of oven dry is 150～200 DEG C, pulverizesParticle diameter be 25～35 μ m.
2. cell positive material according to claim 1, is characterized in that: described phosphoric acid solutionMass percentage concentration be 10～30%.
3. cell positive material according to claim 1, is characterized in that: described lithium hydroxideThe mass percentage concentration of solution is 9.5%.
4. super capacitance cell, is characterized in that: anodal employing anode claimed in claim 1Material.
5. super capacitance cell according to claim 4, is characterized in that: its negative material is adoptedUse graphite type material.
6. super capacitance cell according to claim 5, is characterized in that: described graphite-like materialMaterial comprises one or more in native graphite, Delanium and composite graphite.
7. according to the super capacitance cell described in claim 4～6 any one, it is characterized in that:Its electrolyte is to have the lithium-ion battery electrolytes that decomposition voltage is greater than 7.0V.
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| CN101252043A (en) * | 2007-04-25 | 2008-08-27 | 北京理工大学 | Pre-embedding method of lithium ion super capacitor cathode |
| CN103050290A (en) * | 2012-12-20 | 2013-04-17 | 上海奥威科技开发有限公司 | Internally combined super capacitor |
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| CN101159329A (en) * | 2007-11-12 | 2008-04-09 | 成都中科来方能源科技有限公司 | Composite positive pole material, battery-super electric capacity energy storage means and preparation method |
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