CN101488584A - Asymmetric lithium iron phosphate cell using lithium titanate as main active substance of negative pole - Google Patents
Asymmetric lithium iron phosphate cell using lithium titanate as main active substance of negative pole Download PDFInfo
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- CN101488584A CN101488584A CNA2009100797126A CN200910079712A CN101488584A CN 101488584 A CN101488584 A CN 101488584A CN A2009100797126 A CNA2009100797126 A CN A2009100797126A CN 200910079712 A CN200910079712 A CN 200910079712A CN 101488584 A CN101488584 A CN 101488584A
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- lithium titanate
- powder
- lithium
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- negative pole
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 98
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000013543 active substance Substances 0.000 title claims abstract description 34
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract 4
- 239000000843 powder Substances 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000006258 conductive agent Substances 0.000 claims abstract description 45
- 239000002270 dispersing agent Substances 0.000 claims abstract description 45
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 21
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 21
- 239000006230 acetylene black Substances 0.000 claims abstract description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims description 42
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 41
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 24
- 239000002071 nanotube Substances 0.000 claims description 18
- 239000005955 Ferric phosphate Substances 0.000 claims description 16
- 229940032958 ferric phosphate Drugs 0.000 claims description 16
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 230000004888 barrier function Effects 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052596 spinel Inorganic materials 0.000 claims description 9
- 239000011029 spinel Substances 0.000 claims description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000005234 chemical deposition Methods 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 14
- 239000002033 PVDF binder Substances 0.000 abstract description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 abstract 1
- 239000010405 anode material Substances 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- -1 modified lithium titanate Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 20
- 230000008569 process Effects 0.000 description 18
- 239000010936 titanium Substances 0.000 description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000004087 circulation Effects 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 10
- 229910010710 LiFePO Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000005030 aluminium foil Substances 0.000 description 8
- 238000007766 curtain coating Methods 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000007790 scraping Methods 0.000 description 8
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000010450 olivine Substances 0.000 description 6
- 229910052609 olivine Inorganic materials 0.000 description 6
- 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 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000826915 Saccharum officinarum complex Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 210000004754 hybrid cell Anatomy 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an unsymmetrical lithium iron phosphate battery, the negative pole of which takes lithium titanate as the main active substance, belonging to the technical field of non water electrolysis liquid lithium ion battery or hybrid battery. The battery comprises an anode, a cathode, a diaphragm and electrolyte; wherein the main active substance of the anode is lithium iron phosphate powder, lithium iron titanate powder added with activated carbon or lithium iron phosphate powder added with carbon nanotube, the anode material also comprises caking agent, conductive agent and dispersing agent; the main active substance of the cathode is lithium titanate powder, compound copper, argentum, or lithium titanate powder or semi-conductive modified lithium titanate power, the cathode material also comprises the caking agent, the conductive agent and the dispersing agent. The caking agent is polyvinylidene fluoride, the conductive agent is acetylene black, and the dispersing agent is N-methyl pyrrolidone. The invention has good discharging property under heavy current, and can maintain high specific power and high specific energy.
Description
Technical field
The invention belongs to the lithium ion battery or the hybrid battery technical field of nonaqueous electrolytic solution, particularly a kind of negative pole is the asymmetric ferric phosphate lithium cell of main active substances with the lithium titanate.
Background technology
The lithium titanate of spinel structure is " a zero strain material ", have the excellent cyclical stability and the useful life of overlength, also having good, the safe and specific capacity of anti-over-charging performance and thermal stability simultaneously, big (theoretical specific capacity is 175mAh/g, actual specific capacity can reach 165mAh/g) etc. characteristics, be a kind of novel battery material of excellence.
The olivine-type LiFePO4 is made the positive electrode of lithium ion battery and is reported in 1997 by Goodenough research group at first, this material because have cheap, nontoxic, nonhygroscopic, Environmental compatibility is fine, rich in mineral resources, the battery circulation volume is higher, and (theoretical capacity is 170mAh/g, energy density is 550Wh/kg), stability characteristics such as fine, by vast researcher is paid close attention to.But the charge/discharge capacity of LiFePO4 under high current density is very low.
Make the charge/discharge capacity of battery under high current density of active material in order to improve LiFePO4, adopt the notion of hybrid battery.Along with the development of lithium-ion electric pool technology, the Amatucci of calendar year 2001 U.S. Telcordia Technologies company has reported the AC/Li of active carbon and the combination of lithium ion battery intercalation materials of li ions
4Ti
5O
12Asymmetric hybrid battery uses nonaqueous electrolytic solution, and positive and negative electrode relies on Faraday pseudo-capacitance and lithium ion to embed/take off the machine-processed energy storage of embedding respectively.This prototype battery charging and discharging speed and cyclical stability and ultracapacitor are similar, and energy density has reached 20Wh/kg, is higher than common ultracapacitor.When hybrid battery uses battery and capacitor electrode material at the same time, combine the big and big advantage of power density of energy density that these two kinds of traditional energy storage devices have.In contrast to other new forms of energy device, such as fuel cell and solar cell, hybrid battery has more advantage based on traditional energy storage technology development of maturation.
Summary of the invention
The purpose of this invention is to provide the asymmetric ferric phosphate lithium cell that a kind of negative pole is main active substances with the lithium titanate.
A kind of negative pole is the asymmetric ferric phosphate lithium cell of main active substances with the lithium titanate, comprise positive pole, negative pole, barrier film and electrolyte, it is characterized in that, the main active substances of described positive pole is an iron phosphate powder, add the iron phosphate powder of active carbon or the iron phosphate powder of interpolation carbon nano-tube, positive electrode also comprises binding agent, conductive agent and dispersant, wherein, each material proportion is closed and is active carbon or carbon nano-tube: iron phosphate powder: binding agent: conductive agent: g:(8~10 dispersant=(0~30) g:(50~80)) g:(10~12) g:(0.6~0.8) L; The main active substances of described negative pole is the lithium titanate powder of lithium titanate powder, lithium titanate powder, complex copper, silver or the carbon nano-tube of adding carbon nano-tube or the lithium titanate powder of partly leading modification, negative material also comprises binding agent, conductive agent and dispersant, wherein, each material proportion is closed and is copper, silver or carbon nano-tube: lithium titanate powder: binding agent: conductive agent: g:(8~10 dispersant=(0~30) g:(50~80)) g:(10~12) g:(0.6~0.8) L.
Described binding agent is a Kynoar.
Described conductive agent is an acetylene black.
Described dispersant is the N-methyl pyrrolidone.
Described complex copper, the potassium titanate powder of silver or carbon nano-tube is at the lithium titanate powder of particle surface clad metal silver or copper or be wound with the lithium titanate nanotube of carbon nano-tube, wherein, the lithium titanate powder of compound silver or copper is by lithium titanate powder and liquor argenti nitratis ophthalmicus or copper-bath, acetaldehyde or hydrazine hydrate, and ammoniacal liquor prepares by chemical deposition, the lithium titanate nanotube of composite carbon nanometer tube is with titanium dioxide, sodium hydroxide solution and salpeter solution are that raw material is when carrying out Hydrothermal Preparation lithium titanate nanotube, carbon nano-tube is added in the reactor with raw material, obtains the lithium titanate nanotube of composite carbon nanometer tube.
Described lithium titanate powder of partly leading modification is for being raw material with metatitanic acid and titanium dioxide, mixture was calcined 3~5 hours at 700~850 ℃ behind ball milling, product after reaction finishes under nitrogen atmosphere through 300~500 ℃ of heat treatments 2~4 hours, with stove cooling, the lithium titanate powder of partly being led modification.
Described iron phosphate powder is the olivine-type iron phosphate powder.
Described lithium titanate powder is the spinel type lithium titanate powder.
Beneficial effect of the present invention is: the battery among the present invention is asymmetric hybrid battery, anodal main active substances is an iron phosphate powder, add the iron phosphate powder of active carbon or the iron phosphate powder of interpolation carbon nano-tube, the main active substances of negative pole is a potassium titanate powder, add the lithium titanate powder of carbon nano-tube, complex copper, the lithium titanate powder of silver or carbon nano-tube or the lithium titanate powder of partly leading modification, mix the hybrid battery of the LiFePO4 of active carbon as positive pole, its charge-discharge performance under the big electric current than existing be that the charge-discharge performance of capacitor under big electric current of electrode is good with active carbon and lithium titanate, can under fast charging and discharging, keep high-specific-power and high-energy-density simultaneously, be fit to be applied in aspects such as electric automobile.
Description of drawings
Fig. 1 is the charging/discharging voltage curve of the hybrid battery of assembling among the embodiment 1;
Fig. 2 is the constant current charge-discharge cycle performance curve of the hybrid battery of assembling among the embodiment 1;
Fig. 3 is the cyclic voltammetry curve of the hybrid battery of assembling among the embodiment 1;
Fig. 4 is a charging/discharging voltage curve of executing the hybrid battery of assembling in the example 2;
Fig. 5 is the constant current charge-discharge cycle performance curve of the hybrid battery of assembling among the embodiment 2;
Fig. 6 is the charging/discharging voltage curve of the hybrid battery of assembling among the embodiment 3;
Fig. 7 is the constant current charge-discharge cycle performance curve of the hybrid battery of assembling among the embodiment 3;
Fig. 8 is the charging/discharging voltage curve of the hybrid battery of assembling among the embodiment 4;
Fig. 9 is the constant current charge-discharge cycle performance curve of the hybrid battery of assembling among the embodiment 4.
Embodiment
The invention will be further described below in conjunction with accompanying drawing:
Embodiment 1
The preparation of iron phosphate powder is with reference to " a kind of polycrystalline LiFePO of olivine structural
4Powder preparation method " (publication number: CN1410349) with " a kind of LiFePO
4The preparation method of spherical powder " (publication number: CN1648036), iron phosphate powder adopts following method preparation: at first press LiFePO
4In the mole proportioning of each atom, 0.5:1:1 takes by weighing raw material Li in molar ratio
2CO
3, Fe (CO
2)
22H
2O and NH
4H
2PO
4, with raw material ball milling 6 hours and oven dry, about 400 ℃ of The pre-heat treatment are 8 hours under the weakly reducing atmosphere environment, take out after cooling to room temperature with the furnace, and secondary ball milling 6 hours, dry, sieve.For the tap density that increases material to improve the battery volume energy density, powder is carried out mist projection granulating, put it into porcelain boat subsequently, 700 ℃ of roastings 8 hours, take out after cooling to room temperature with the furnace, obtain the LiFePO of olivine structural
4Powder (particle diameter is about 5~20 μ m).
A kind of negative pole is the asymmetric ferric phosphate lithium cell of main active substances with the lithium titanate, comprise positive pole, negative pole, barrier film and electrolyte, the main active substances of described positive pole is for adding the olivine-type iron phosphate powder of active carbon, positive electrode also comprises binding agent, conductive agent and dispersant, wherein, each material proportion is closed, active carbon: iron phosphate powder: binding agent: conductive agent: dispersant=30g:50g:10g:10g:0.7L, described binding agent is a Kynoar, described conductive agent is an acetylene black, and described dispersant is the N-methyl pyrrolidone.Get the LiFePO of the spherical olivine structural of above-mentioned preparation
4Powder (particle diameter is about 5~20 μ m) 2.5g, specific area is about 1500m
2The active carbon 1.5g of/g, binding agent Kynoar (PVDF) 0.5g and conductive agent acetylene black 0.5g, mix the back and add dispersant N-methyl pyrrolidone (NMP) 35ml, stirred 4 hours, on aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 120 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The main active substances of described negative pole is that the spinel type lithium titanate powder is (commercially available, the lithium titanate powder is a nanoscale, average grain diameter is about 500nm), negative material also comprises binding agent, conductive agent and dispersant, and wherein, each material proportion is closed and is, lithium titanate powder: binding agent: conductive agent: dispersant=80g:10g:10g:0.8L, described binding agent is a Kynoar, and described conductive agent is an acetylene black, and described dispersant is the N-methyl pyrrolidone.Get spinel-type Li
4Ti
5O
12Powder 4.8g, binding agent Kynoar (PVDF) 0.6g and conductive agent acetylene black 0.6g, mix the back and add dispersant N-methyl pyrrolidone (NMP) 48ml, stirred 4 hours, on aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 120 ℃ of following vacuum to obtain cathode membrane after dry 1.5 hours.
The process of assembling test battery: with positive and negative electrode diaphragm diameter is 12 millimeters drift punching, with assembling CR2032 type button test battery, adopts 1mol/L lithium hexafluoro phosphate (LiPF
6) mixed liquor in ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio of ethylene carbonate and dimethyl carbonate is 1:1) is as electrolyte, it is the barrier film of Sai Er Goethe 2400 (Celgard 2400) that barrier film adopts the U.S. to produce model, packaged battery carries out in the glove box of argon gas atmosphere, makes hybrid battery.
The hybrid battery of present embodiment preparation obtains the charging/discharging voltage curve as shown in Figure 1 through the constant current charge-discharge test, and charge and discharge process comprises A-B, B-C, C-D, E-F, F-G, six processes of G-H.In the A-B stage, along with the carrying out of constant current charge, system voltage constantly raises, and when voltage is elevated to the 1.8V left and right sides, is the B-C stage, and charging is proceeded, and that cell voltage keeps substantially is constant, this moment Li
+Constantly from anodal LiFePO
4In spin off, embed negative pole Li
4Ti
5O
12In.C-D is the last stage of charging, at this moment Li
+Deviate from totally or owing to the reason Li of voltage polarizing
+Can not continue to deviate from from material, in this stage, the voltage of hybrid battery raises along with the rising of specific capacity, is similar to linear relationship, and final charging process finishes.The E-H stage is the discharge overall process, E-F wherein, and F-G, G-H are respectively C-D, the inverse process of B-C and A-B.The constant current charge-discharge cycle performance as shown in Figure 2, along with the raising of charge-discharge magnification, the capacity of battery descends thereupon.Under identical charge-discharge magnification, the circulation repeatedly capacity of back battery also can descend slightly.Discharge capacity in preceding 10 circulations is starkly lower than the charging capacity, and the discharging efficiency of battery in back tens circulations is all more than 95%.Record cyclic voltammetry curve as shown in Figure 3 through cyclic voltammetry, sweep limits is 1.0-3.5V, and sweep speed is 0.01V/s.Hybrid battery is the Faraday pseudo-capacitance characteristic, at 1.5V and 2.2V a pair of redox peak than broad is arranged.
Embodiment 2
A kind of negative pole is the asymmetric ferric phosphate lithium cell of main active substances with the lithium titanate, comprise positive pole, negative pole, barrier film and electrolyte, the main active substances of described positive pole is for adding the olivine-type iron phosphate powder of active carbon, positive electrode also comprises binding agent, conductive agent and dispersant, wherein, each material proportion is closed, active carbon: iron phosphate powder: binding agent: conductive agent: dispersant=10g:70g:10g:10g:0.7L, described binding agent is a Kynoar, described conductive agent is an acetylene black, and described dispersant is the N-methyl pyrrolidone.Get the LiFePO of spherical olivine structural
4Powder (LiFePO
4Powder diameter is about 5~20 μ m, and the preparation method is identical with embodiment 1) 3.5g, specific area is about 1500m
2The active carbon 0.5g of/g, binding agent Kynoar (PVDF) 0.5g and conductive agent acetylene black 0.5g, mix the back and add dispersant N-methyl pyrrolidone (NMP) 35ml, stirred 4 hours, on aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 120 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The main active substances of described negative pole is the spinel type lithium titanate powder of partly leading modification, (with metatitanic acid and titanium dioxide is raw material, mixture was calcined 4 hours at 800 ℃ behind ball milling, product after reaction finishes under nitrogen atmosphere through 400 ℃ of heat treatments 2 hours, cool off with stove, partly led the lithium titanate powder of modification, the lithium titanate powder of partly leading modification is a nanoscale, average grain diameter is about 500nm), negative material also comprises binding agent, conductive agent and dispersant, wherein, it is that lithium titanate powder: binding agent: conductive agent: dispersant=80g:10g:10g:0.8L, described binding agent are Kynoar that each material proportion is closed, described conductive agent is an acetylene black, and described dispersant is the N-methyl pyrrolidone.Learn from else's experience nitrogen atmosphere second lead the spinel-type Li of modification
4Ti
5O
12Powder 4.8g, binding agent Kynoar (PVDF) 0.6g and conductive agent acetylene black 0.6g, mix the back and add dispersant N-methyl pyrrolidone (NMP) 48ml, stirred 4 hours, on aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 120 ℃ of following vacuum to obtain cathode membrane after dry 1.5 hours.
The process of assembling test battery: with positive and negative electrode diaphragm diameter is 12 millimeters drift punching, with assembling CR2032 type button test battery, adopts 1mol/L lithium hexafluoro phosphate (LiPF
6) mixed liquor in ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio of ethylene carbonate and dimethyl carbonate is 1:1) is as electrolyte, it is the barrier film of Sai Er Goethe 2400 (Celgard 2400) that barrier film adopts the U.S. to produce model, packaged battery carries out in the glove box of argon gas atmosphere, obtains (the LiFePO that positive pole contains 10% active carbon
4-AC)/Li
4Ti
5O
12Hybrid battery.
The hybrid battery for preparing in the present embodiment obtains the charging/discharging voltage curve as shown in Figure 4 through the constant current charge-discharge test, and similar with Fig. 1, charge and discharge process also comprises A-B, B-C, C-D, E-F, F-G, six processes of G-H, E-F wherein, F-G, G-H are respectively C-D, the inverse process of B-C and A-B.As can be seen, the battery in the embodiment 1, the voltage platform of this battery is longer more flat.The constant current charge-discharge cycle performance as shown in Figure 5, and is similar with Fig. 2, and along with the raising of charge-discharge magnification, the capacity of battery descends thereupon.Under identical charge-discharge magnification, the circulation repeatedly capacity of back battery also can descend slightly.Discharge capacity in preceding 10 circulations is starkly lower than the charging capacity, and the discharging efficiency of battery in back tens circulations is all more than 95%.
Embodiment 3
A kind of negative pole is the asymmetric ferric phosphate lithium cell of main active substances with the lithium titanate, comprise positive pole, negative pole, barrier film and electrolyte, the main active substances of described positive pole is the olivine-type iron phosphate powder, positive electrode also comprises binding agent, conductive agent and dispersant, wherein, each material proportion is closed, iron phosphate powder: binding agent: conductive agent: dispersant=80g:10g:10g:0.67L, described binding agent is a Kynoar, described conductive agent is an acetylene black, and described dispersant is the N-methyl pyrrolidone.Get the LiFePO of spherical olivine structural
4Powder (LiFePO
4Powder diameter is about 5~20 μ m, the preparation method is identical with embodiment 1) 4.8g, binding agent Kynoar (PVDF) 0.6g and conductive agent acetylene black 0.6g, mix the back and add dispersant N-methyl pyrrolidone (NMP) 40ml, stirred 4 hours, on aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 120 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The main active substances of described negative pole is that (with metatitanic acid and titanium dioxide is raw material for the spinel type lithium titanate powder of compound silver, mixture was calcined 4 hours at 800 ℃ behind ball milling, obtaining the lithium titanate powder, is the spinel-type Li of 0.01mol/L liquor argenti nitratis ophthalmicus, pH value compound 8% (weight) silver that to be 8~9 weak aqua ammonia and acetaldehyde obtain by chemical deposition with lithium titanate powder and concentration
4Ti
5O
12Powder, the spinel type lithium titanate powder of the compound silver that obtains is a nanoscale, average grain diameter is 500nm), negative material also comprises binding agent, conductive agent and dispersant, and wherein, each material proportion is closed and is, silver: lithium titanate powder: binding agent: conductive agent: dispersant=6.4:73.6g:10g:10g:0.8L, described binding agent is a Kynoar, and described conductive agent is an acetylene black, and described dispersant is the N-methyl pyrrolidone.Get the spinel-type Li of compound silver
4Ti
5O
12Powder 4.8g, binding agent Kynoar (PVDF) 0.6g and conductive agent acetylene black 0.6g, mix the back and add dispersant N-methyl pyrrolidone (NMP) 48ml, stirred 4 hours, on aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 120 ℃ of following vacuum to obtain cathode membrane after dry 1.5 hours.
The process of assembling test battery: with positive and negative electrode diaphragm diameter is 12 millimeters drift punching, with assembling CR2032 type button test battery, adopts 1mol/L lithium hexafluoro phosphate (LiPF
6) mixed liquor in ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio of ethylene carbonate and dimethyl carbonate is 1:1) is as electrolyte, it is the barrier film of Sai Er Goethe 2400 (Celgard 2400) that barrier film adopts the U.S. to produce model, packaged battery carries out in the glove box of argon gas atmosphere, obtains the anodal LiFePO that does not contain active carbon
4/ Li
4Ti
5O
12Hybrid battery.
The hybrid battery for preparing in the present embodiment obtains the charging/discharging voltage curve as shown in Figure 6 through the constant current charge-discharge test, and similar with Fig. 4, charge and discharge process also comprises A-B, B-C, C-D, E-F, F-G, six processes of G-H, E-F wherein, F-G, G-H are respectively C-D, the inverse process of B-C and A-B.Owing to added carbon nano-tube, the voltage platform of battery is not a definite value, but at 1.5V between the 1.9V.The constant current charge-discharge cycle performance as shown in Figure 7, and is similar with Fig. 5, and along with the raising of charge-discharge magnification, the capacity of battery descends thereupon.Under identical charge-discharge magnification, the circulation repeatedly capacity of back battery also can descend slightly.Discharge capacity in preceding 10 circulations is starkly lower than the charging capacity, and the discharging efficiency of battery in back tens circulations is all more than 95%.
Embodiment 4
The preparation method of lithium titanate nanotube is with reference to " the spinel lithium titanate nanotube/line preparation method who is used for lithium battery and capacitor " (publication number: CN1725530): with 5g TiO
2With 70mL concentration is that the NaOH solution of 10m/L mixes, and is 0.2~0.5W/cm at power
2Following sonochemistry reaction 30 minutes, to move into volume then be 100mL, have in the autoclave of teflon lined and carried out hydro-thermal reaction 24 hours, hydrothermal temperature is 150 ℃, after reaction finishes, takes out reactor, naturally cool to room temperature, filtering after opening kettle cover, is that the product to hydro thermal method washed 30 minutes under 2 the condition at pH with the nitric acid of 0.2mol/L concentration, behind the vacuum filtration, product obtains the fluffy powder product of white after 80 ℃ of dryings, be H
2Ti
3O
7Nanotube; With 1.5gH
2Ti
3O
7Nanotube and 40mLLiOH aqueous solution, stir, to move into volume then be 50mL, have in the autoclave of teflon lined and carry out more than the hydro-thermal reaction 24h, preparation nanotube hydrothermal temperature is 100~150 ℃, after reaction finishes, take out reactor, naturally cool to room temperature, filter after opening kettle cover, with deionized water wash for several times, behind the vacuum filtration, filter cake with absolute ethanol washing for several times, product obtains the product of white after 80 ℃ of vacuumize, white product obtains having spinel-type Li through 400 ℃ of heat treatments after 2 hours in air atmosphere
4Ti
5O
12Nanotube, its external diameter is about 10nm, and internal diameter is 4~5nm, is about the hundreds of nanometer to micron order.
A kind of negative pole is the asymmetric ferric phosphate lithium cell of main active substances with the lithium titanate, comprise positive pole, negative pole, barrier film and electrolyte, the main active substances of described positive pole is the olivine-type iron phosphate powder, positive electrode also comprises binding agent, conductive agent and dispersant, wherein, each material proportion is closed, iron phosphate powder: binding agent: conductive agent: dispersant=80g:10g:10g:0.6L, described binding agent is a Kynoar, described conductive agent is an acetylene black, and described dispersant is the N-methyl pyrrolidone.Get the LiFePO of spherical olivine structural
4Powder (LiFePO
4The preparation method of powder is identical with embodiment 1) 4.0g, binding agent Kynoar (PVDF) 0.5g and conductive agent acetylene black 0.5g, mix the back and add dispersant N-methyl pyrrolidone (NMP) 30ml, stirred 4 hours, on aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 120 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The main active substances of described negative pole is spinel type lithium titanate powder (a lithium titanate nanotube), negative material also comprises binding agent, conductive agent and dispersant, wherein, each material proportion is closed, lithium titanate powder: binding agent: conductive agent: dispersant=80g:10g:10g:0.8L, described binding agent is a Kynoar, and described conductive agent is an acetylene black, and described dispersant is the N-methyl pyrrolidone.Get the spinel-type Li that adopts method for preparing
4Ti
5O
12(its external diameter is about 10nm to lithium titanate nanotube 4.0g, internal diameter is 4~5nm, be about the hundreds of nanometer to micron order), binding agent Kynoar (PVDF) 0.5g and conductive agent acetylene black 0.5g, mix the back and add dispersant N-methyl pyrrolidone (NMP) 40ml, carry out ultrasonicly in supersonic generator, ultrasonic power is 0.2~0.5W/cm
2, 1 hour time, stirred then 4 hours, on aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 120 ℃ of following vacuum to obtain cathode membrane after dry 1.5 hours.
The process of assembling test battery: with positive and negative electrode diaphragm diameter is 12 millimeters drift punching, with assembling CR2032 type button test battery, adopts 1mol/L lithium hexafluoro phosphate (LiPF
6) mixed liquor in ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio of ethylene carbonate and dimethyl carbonate is 1:1) is as electrolyte, it is the barrier film of Sai Er Goethe 2400 (Celgard 2400) that barrier film adopts the U.S. to produce model, packaged battery carries out in the glove box of argon gas atmosphere, obtains negative pole and uses Li
4Ti
5O
12The LiFePO of nanotube
4/ Li
4Ti
5O
12Hybrid battery.
The hybrid battery for preparing in the present embodiment obtains the charging/discharging voltage curve as shown in Figure 8 through the constant current charge-discharge test, and similar with Fig. 6, charge and discharge process also comprises A-B, B-C, C-D, E-F, F-G, six processes of G-H, E-F wherein, F-G, G-H are respectively C-D, the inverse process of B-C and A-B.Because negative pole adopts the lithium titanate nanotube, the voltage platform of battery is not a definite value, but at 1.5V between the 2.2V.The constant current charge-discharge cycle performance as shown in Figure 9, and is similar with Fig. 7, and along with the raising of charge-discharge magnification, the capacity of battery descends thereupon.Under identical charge-discharge magnification, the circulation repeatedly capacity of back battery also can descend slightly.
Claims (8)
1, a kind of negative pole is the asymmetric ferric phosphate lithium cell of main active substances with the lithium titanate, comprise positive pole, negative pole, barrier film and electrolyte, it is characterized in that, the main active substances of described positive pole is an iron phosphate powder, add the iron phosphate powder of active carbon or the iron phosphate powder of interpolation carbon nano-tube, positive electrode also comprises binding agent, conductive agent and dispersant, wherein, each material proportion is closed and is active carbon or carbon nano-tube: iron phosphate powder: binding agent: conductive agent: g:(8~10 dispersant=(0~30) g:(50~80)) g:(10~12) g:(0.6~0.8) L; The main active substances of described negative pole is the lithium titanate powder of lithium titanate powder, lithium titanate powder, complex copper, silver or the carbon nano-tube of adding carbon nano-tube or the lithium titanate powder of partly leading modification, negative material also comprises binding agent, conductive agent and dispersant, wherein, each material proportion is closed and is copper, silver or carbon nano-tube: lithium titanate powder: binding agent: conductive agent: g:(8~10 dispersant=(0~30) g:(50~80)) g:(10~12) g:(0.6~0.8) L.
2, a kind of negative pole according to claim 1 asymmetric ferric phosphate lithium cell that is main active substances with the lithium titanate is characterized in that described binding agent is a Kynoar.
3, a kind of negative pole according to claim 1 asymmetric ferric phosphate lithium cell that is main active substances with the lithium titanate is characterized in that described conductive agent is an acetylene black.
4, a kind of negative pole according to claim 1 asymmetric ferric phosphate lithium cell that is main active substances with the lithium titanate is characterized in that described dispersant is the N-methyl pyrrolidone.
5, a kind of negative pole according to claim 1 is the asymmetric ferric phosphate lithium cell of main active substances with the lithium titanate, it is characterized in that, described complex copper, the lithium titanate powder of silver or carbon nano-tube is at the lithium titanate powder of particle surface clad metal silver or copper or be wound with the lithium titanate nanotube of carbon nano-tube, wherein, the lithium titanate powder of compound silver or copper is by lithium titanate powder and liquor argenti nitratis ophthalmicus or copper-bath, acetaldehyde or hydrazine hydrate, and ammoniacal liquor prepares by chemical deposition, the lithium titanate nanotube of composite carbon nanometer tube is with titanium dioxide, sodium hydroxide solution and salpeter solution are that raw material is when carrying out Hydrothermal Preparation lithium titanate nanotube, carbon nano-tube is added in the reactor with raw material, obtains the lithium titanate nanotube of composite carbon nanometer tube.
6, a kind of negative pole according to claim 1 asymmetric ferric phosphate lithium cell that is main active substances with the lithium titanate, it is characterized in that, described lithium titanate powder of partly leading modification is for being raw material with metatitanic acid and titanium dioxide, mixture was calcined 3~5 hours at 700~850 ℃ behind ball milling, product after reaction finishes under nitrogen atmosphere through 300~500 ℃ of heat treatments 2~4 hours, with stove cooling, the lithium titanate powder of partly being led modification.
7, a kind of negative pole according to claim 1 asymmetric ferric phosphate lithium cell that is main active substances with the lithium titanate is characterized in that described iron phosphate powder is the olivine-type iron phosphate powder.
8, be the asymmetric ferric phosphate lithium cell of main active substances with the lithium titanate according to claim 1,5 or 6 described a kind of negative poles, it is characterized in that described lithium titanate powder is the spinel type lithium titanate powder.
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