CN101154727A - Coating method of porous clad material for effectively improving rate performance of lithium nickel cobalt manganese oxygen - Google Patents
Coating method of porous clad material for effectively improving rate performance of lithium nickel cobalt manganese oxygen Download PDFInfo
- Publication number
- CN101154727A CN101154727A CNA2007100357466A CN200710035746A CN101154727A CN 101154727 A CN101154727 A CN 101154727A CN A2007100357466 A CNA2007100357466 A CN A2007100357466A CN 200710035746 A CN200710035746 A CN 200710035746A CN 101154727 A CN101154727 A CN 101154727A
- Authority
- CN
- China
- Prior art keywords
- solution
- coating
- lithium nickel
- nickel cobalt
- cobalt manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 69
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000000576 coating method Methods 0.000 title claims description 31
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 6
- 229910013716 LiNi Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000009938 salting Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract 2
- 238000012856 packing Methods 0.000 abstract 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 23
- 239000003792 electrolyte Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 230000004087 circulation Effects 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910018626 Al(OH) Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 229910018085 Al-F Inorganic materials 0.000 description 2
- 229910018179 Al—F Inorganic materials 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical compound [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- CPABIEPZXNOLSD-UHFFFAOYSA-N lithium;oxomanganese Chemical compound [Li].[Mn]=O CPABIEPZXNOLSD-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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
Abstract
The invention discloses a packing method for multiaperture packing material for improving multiplying power performance of lithium nickel cobalt manganese oxygen, which is characterized in that the method comprises following steps: (1) soluble aluminum salt solution of corresponding matter mass is prepared according to Al/LiNi1/3Co1/3Mn1/3O2 moore ratio of 0.5 percent to 3.0 percent, added into the water solution of anode material LiNi1/3Co1/3Mn1/3O2, stirred and mixed evenly; (2) ammonium hydrogen fluoride solution of corresponding matter mass is prepared according to F/Al moore ratio of 3 to 6 and dipped into the solution in (1), stirred and mixed evenly until final reaction; (3) the solution of (2) is arranged statically for 2h to 5h, filtered by vacuum, dried the deposit and put into muffle to bake, the air in the stove is argon (can be nitrogen) and the anode material active matter power packed with multiaperture AlF3 film under the calcinations temperature of 200 DEG C to 650 DEG C.
Description
Technical field
The present invention relates to materials chemistry field and high-energy battery material technology, be specifically related to a kind of novel lithium ion battery anode material lithium nickel cobalt manganese oxygen (LiNi
1/3Co
1/3Mn
1/3O
2) the method for coating of porous clad material.
Background technology:
Lithium ion battery has that volume is little, light weight, specific capacity are big, have extended cycle life, advantages such as self discharge is little, memory-less effect.Be widely used in fields such as portable Move tool, digital product, artificial satellite, Aero-Space at present, also had boundless prospect in fields such as electric bicycle and automobiles.LiNi
1/3Co
1/3Mn
1/3O
2Had both the advantage that lithium bores oxygen, lithium nickel oxygen, lithium manganese oxygen preferably, and remedied deficiency separately to a certain extent, characteristics such as have height ratio capacity, stable cycle performance, cost is relatively low, security performance is better, be considered to be used for the ideal selection of mixed type electrical source of power (HEV), also be considered to the best positive electrode that can replace lithium cobalt oxygen.Therefore, the research of this series material becomes present focus.
Yet discover, with respect to lithium cobalt oxygen, LiNi
1/3Co
1/3Mn
1/3O
2High rate performance not good, become restriction this material further key in application.Preparation method's innovation and finishing are considered to improve the important channel of material electrochemical performance.Finishing refers to coat the stable film substrate of one deck on the surface of material, so that improve the cyclical stability of material.Such film substrate is mainly metal oxide or hydroxide.Present SiO
2, MgO, Al
2O
3, ZrO
2, ZnO, Li
2O-B
2O
3Be widely used in LiCoO Deng oxide
2, LiMn
2O
4, LiNiO
2And their compound, wherein Al
2O
3Be maximum clad material of using, but select suitable clad material, with LiNi
1/3Co
1/3Mn
1/3O
2For matrix coats, and it is few effectively to improve the correlative study of its high rate performance.And great majority studies show that the coating layer of common densification is not very outstanding for the high rate capability effect that improves material.
When lithium battery discharged and recharged under high magnification, electrolyte was very active, is easy to generate HF, and HF can dissolve the both positive and negative polarity active material, causes the quick decay of capacity.People such as Li [J.Power Sources, 160 (2006) 1342] adopt spray drying process to LiNi
1/3Co
1/3Mn
1/3O
2Carry out ZrO
2Coating research, found that the stable circulation performance of material under 0.5C and 2C being significantly increased all after the coating than original material.People such as Myung [Chem.Mater, 17 (2005) 3695] find Al
2O
3Coating layer is at Li[Li
0.05Ni
0.4Co
0.15Mn
0.4] O
2Played the effect of HF catcher, by being reflected at Al
2O
3Can further form AlF on the coating layer
3Thereby, suppress the side reaction of material and electrolyte better.People such as Jang [Electrochimica Acta, 50 (2005) 4168] adopt the precipitation method at LiNi
1/3Co
1/3Mn
1/3O
2Last coating one deck Al (OH)
3, this material is respectively 96%, 92% with 45 the circulation back capability retentions under 1/8C of clad material not, and effect is not clearly, but high rate capability has bright raising, and capacity can remain on 80% 0.1C under under the 2C, and not only 45% of coating.The author thinks Al (OH)
3Can form the Al-F compound with the HF that electrolyte discharges, such as AlF
33H
2O etc. will suppress the side reaction of active component in the material preferably.Sun etc. [Electrochemistry Communications, 8 (2006) 821] are that raw material is at LiCoO with ammonium fluoride and aluminum nitrate
2Coated AlF on the matrix
3, found that the capability retention of material and high rate performance have obtained bigger raising.From above-mentioned research as can be seen,, can reduce contacting of positive active material and electrolyte, prevent the dissolving of positive electrode, can also suppress the decomposition of electrolyte under the high potential simultaneously though suitable clad material can not change the ion channel of material.Particularly under high magnification charged and discharged condition, suitable coating layer can suppress the side reaction of electrolyte and electrode material effectively, thereby had greatly improved the chemical property of material under the high magnification condition.
In sum, we infer at LiNi
1/3Co
1/3Mn
1/3O
2Coat Al (OH) on the matrix
3Or Al
2O
3In fact may be AlF
3Playing significant feature, so we propose at LiNi
1/3Co
1/3Mn
1/3O
2The surface coats one deck porous Al F
3The method for coating of book film, result of the test find, the porous Al F that is prepared by method of the present invention
3The book film can improve the chemical property of basis material under the high magnification condition effectively, has improved its cyclical stability and cycle life.
Summary of the invention
Purpose of the present invention aim to provide a kind of easy to operate, step is simple, production cost is low, be fit to the method for coating of suitability for industrialized production, at LiNi
1/3Co
1/3Mn
1/3O
2Successfully coat on the matrix and go up novel porous material, to improve LiNi
1/3Co
1/3Mn
1/3O
2The chemical property of material, thus further increase substantially the competitiveness of such material on market.
The novel clad material that the present invention proposes is the AlF with loose structure
3, be used to coat anode material of lithium battery LiNi
1/3Co
1/3Mn
1/3O
2, to improve its multiplying power discharging property and cycle life; The method for coating that is adopted is a kind of chemical precipitation-high-temperature calcination.The present invention includes following steps:
(1) presses Al/LiNi
1/3Co
1/3Mn
1/3O
2Mol ratio is the soluble aluminum salting liquid of 0.5%～3.0% preparation homologue quality, joins positive electrode LiNi
1/3Co
1/3Mn
1/3O
2The aqueous solution in, stir mixing;
(2) by the F/Al mol ratio be 3～6, the ammonium hydrogen fluoride solution of preparation homologue quality splashes into ammonium hydrogen fluoride solution in (1) described solution, stirs, mixing finishes to reaction;
(3) behind the solution left standstill 2～5h with (2) step gained, through vacuum filtration, the precipitation that obtains after the drying, is put into the Muffle furnace roasting, and furnace atmosphere is argon gas or nitrogen, and calcining heat is 200 ℃～650 ℃, obtains having coated porous Al F
3The active substances in cathode materials powder of book film.
The present invention selects for use aluminum soluble salt and ammonium acid fluoride as raw material, reaches preparation porous Al F by control F/Al mol ratio
3The purpose of book film, described F/Al mol ratio preferable range is 3.5～4.5.
(3) going on foot described roasting time is 1～8h.
Al/LiNi
1/3Co
1/3Mn
1/3O
2Mol ratio most preferably is 1.5%.
Described soluble aluminum salting liquid is a kind of in aluminum nitrate solution, aluminum sulfate solution, aluminium acetate solution, the liquor alumini chloridi.
The principle of invention is:
Because positive electrode LiNi
1/3Co
1/3Mn
1/3O
2The disappearance that in preparation process, causes anion oxygen through high-temperature calcination, make substrate material surface have defective and stress, being easy to generate structure in high magnification charge and discharge process caves in and produces bigger capacity attenuation, coat and modification by the surface, can eliminate the stress that the surface exists on the one hand, be coated on its surperficial book film on the other hand and can effectively stop its surperficial defective to contact, thereby improve its surface stability with HF in the electrolyte; AlF
3Being a kind of colourless or white ionic compound, is the ionic crystals with six side's layer structures, AlF
3(K
Sp=1.0 * 10
-15) solubility is very little in water, because AlF
3In the Al-F key strong, be not easy fracture, Stability Analysis of Structures is if form the AlF of one deck densification at matrix surface
3The book film then can stop the corrosion of HF in the electrolyte effectively; But, fine and close AlF
3The book film is unfavorable for that the transmission of lithium ion and electric charge shift, and therefore, are necessary to design and prepare the AlF with microcellular structure
3The book film, this is the key of dealing with problems.
In the aqueous solution, under alkalescence and acid condition, Al
3+Existence is suc as formula the hydrolysis of (1) and (2);
Al(OH)
3(s)＝Al
3+(aq)+3OH
-(aq) K
sp(b)＝2×10
-33 (1)
Al(OH)
3(s)+H
2O(l)＝H
+(aq)+Al(OH)
4 - K
sp(a)＝2×10
-11 (2)
As raw material, at first, the soluble aluminum salting liquid is joined positive electrode LiNi with aluminum soluble salt and ammonium acid fluoride
1/3Co
1/3Mn
1/3O
2 -The aqueous solution in, part A l
3+Hydrolysis takes place, and produces precipitation of hydroxide; Then, dropwise add ammonium hydrogen fluoride solution, fluorine becomes two parts of complex reaction and precipitation reaction with the reaction decomposes of aluminium, and wherein complex reaction is nearly 6 grades.When the reaction of fluorine and aluminium begins, F in the solution
-Concentration is lower, part A l
3+Hydrolysis takes place, produce precipitation of hydroxide, along with the carrying out that drips, F
-Equilibrium concentration increase original and Al gradually
3+The hydroxide ion of reaction is by F
-Replace Al
3+Hydrolysis be suppressed each Al
3+Only with 1 to 3 F
-Complex reaction takes place, and forms AlF
2+, AlF
2 +And AlF
3, AlF
3Precipitation forms AlF with hydrone
33H
2O nucleus, nucleus continue to grow up into crystal grain, and numerous crystal grain is closely heaped and formed fine and close AlF
33H
2O book film;
Along with the carrying out that ammonium hydrogen fluoride solution drips, F
-Equilibrium concentration further increase part A lF gradually
3Reaction suc as formula (3) then takes place:
AlF
3+3F
-＝[AlF
6]
3- β
6＝7.0×10
19 (3)
Make it to form [AlF
6]
3-, and be partly dissolved gradually, thereby at the AlF of densification
33H
2Original position forms porous Al F on the O book film
33H
2O book film.
The advantage and the good effect of invention
The present invention has following distinguishing feature:
1) the present invention utilizes AlF
3Design feature and special physico-chemical property, the novel porous AlF of preparation is proposed
3Method as a kind of clad material is used for LiNi
1/3Co
1/3Mn
1/3O
2Study on the modification, prepared by method of the present invention at LiNi
1/3Co
1/3Mn
1/3O
2Material surface coats the AlF of one deck porous
3The book film, the porosity of book film is excessive F by the F/Al mol ratio
-Concentration control because at the AlF that adopts this method preparation
3Book film surface, a small amount of AlF
3Because of having formed [AlF
6]
3-And dissolving gradually, thereby at AlF
3Book film surface has formed many micropores, and this surface has produced the AlF of many micropores
3The book film not only can effectively stop in the electrolyte micro-HF to the decorations of invading of basis material, and because the existence of many micropores also helps the transmission and electric charge transfer of lithium ion, thereby can further improve positive electrode LiNi
1/3Co
1/3Mn
1/3O
2Surface stability and multiplying power discharging property.
2) the present invention adopts chemical precipitation-high-temperature calcination to coat, prepared porous Al F
3The book film is successfully with AlF
3Be coated to LiNi
1/3Co
1/3Mn
1/3O
2Material surface, this method for coating is simple to operate, and technology is easy to control, and production cost is low, and manufacturing cycle is short, is easy to realize large-scale industrial production.
3) among the present invention through porous Al F
3LiNi after the coating
1/3Co
1/3Mn
1/3O
2, under higher multiplying power, the specific capacity after the coating will be higher than the specific capacity before coating, and cyclical stability and cycle life improve greatly.
The preparation-obtained porous Al F of the present invention
3Clad material is used for LiNi
1/3Co
1/3Mn
1/3O
2Study on the modification, at LiNi
1/3Go
1/3Mn
1/3O
2Substrate material surface coats the AlF that one deck has loose structure
3The book film, owing to effectively stoped in the electrolyte micro-HF to the decorations of invading of basis material, strengthened the stability of substrate material surface, improved material effectively than the chemical property under the high magnification, the inventive method will increase substantially the competitiveness of such material on market.Simultaneously, do not count thinking also with for providing reference about the selection of clad material and the design of method for coating in the materials chemistry field from now among the present invention.
Description of drawings
Fig. 1 AlF
3LiNi before and after coating
1/3Co
1/3Mn
1/3O
2The XRD of material.
Fig. 2 AlF
3Coat back LiNi
1/3Co
1/3Mn
1/3O
2The TEM of material
Fig. 3 is with AlF
3Material be a positive pole before and after coating, and the lithium sheet is the half-cell of negative pole preceding 80 times circulation volume figure under the 2C multiplying power.
Fig. 4 is with AlF
3Material be a positive pole before and after coating, and the lithium sheet is the half-cell of negative pole preceding 50 times circulation volume figure under the 5C multiplying power.
Embodiment
The invention will be further described by the following examples.
Embodiment 1
At first accurately take by weighing 0.051g NH
4HF
2, the NH of preparation 0.005mol/L
4HF
2Solution.Take by weighing 3.0g basis material LiNi
1/3Co
1/3Mn
1/3O
2With 0.200g Al (NO
3)
312H
2O puts into the beaker of 500ml, adds the redistilled water of 100ml, is placed on and fully stirs 10min on the magnetic stirring apparatus.Low whipping speed is 300r/min, and temperature is under 45 ℃, with buret with the rate of titration of 1.5ml/min to basis material and Al (NO
3)
312H
2Drip the NH of preparation in the mixed liquor of O
4HF
2Solution (the F/Al mol ratio is about 3.8).After precipitation is complete turbid solution is left standstill 2～3h.Through vacuum filtration, the air dry oven that is deposited in that obtains descends dry 3h for 110 ℃, obtains powder.Powder is placed 250 ℃ of roasting 3h under argon gas atmosphere of Muffle furnace, and then at 600 ℃ of roasting 6h.Obtain coating AlF
3Target material.Its structure comparison diagram is seen Fig. 1.As shown in Figure 1, the x-ray diffraction pattern of the material after basis material and the coating is closely similar, illustrates to coat AlF
3The back does not have significantly influence to the structure of basis material.Covered effect is seen Fig. 2.Transmission electron microscope shows that it is more even to have formed one deck on basis material, the nanoscale AlF of band micropore
3The coating layer film, thickness is about 2nm.
Target material, acetylene black and the polytetrafluoroethylene (PTFE) binding agent of preparation are fully mixed in the ratio (85: 10: 5) of certain mass, after 80～100 ℃ of down dry 24h eliminate moisture in container, be applied on the stainless (steel) wire, depress to the uniform cathode film of thickness at the pressure of 20kPa with hydraulic press.With the metal lithium sheet is negative pole, and electrolyte is 1mol/L LiPF
6EC: DMC: EMC/1: 1: 1 (w/w) mixed solution, moisture is less than 9.34 * 10
-6G/L, free acid HF content is less than 2.55 * 10
-6G/L.Assembling button half-cell (CR2032) in inert atmosphere glove box (UNILAB MBRAUN Germany produces), glove box operating system is high-purity Ar atmosphere, the content of water and oxygen is all less than 1 * 10
-6G/L, the simulated battery that assembles is at room temperature tested.The material of Bao Fuing is not by the same method assembled battery, so that compare research.Detect its charge/discharge capacity under 2C and 5C and cyclical stability respectively with blue electric tester.Adopt the pattern that constant current is filled, constant voltage is filled, constant current is put, the charging/discharging voltage scope is 2.8～4.3V.Fig. 3 is with AlF
3Material be a positive pole before and after coating, and the lithium sheet is the half-cell of negative pole preceding 80 times circulation volume figure under the 2C multiplying power; Fig. 4 is with AlF
3Material be a positive pole before and after coating, and the lithium sheet is the half-cell of negative pole preceding 50 times circulation volume figure under the 5C multiplying power.As can be seen from Figure 3, the capability retention of the material before coating under the 2C multiplying power after preceding 80 circulations only is 54.1%, and the material capacity conservation rate after coating illustrates to coat AlF near 100%
3After improved basis material greatly than cycle life under the high magnification.As can be seen from Figure 4, at high magnification more, under the 5C multiplying power, 50 capacity of material circulation after the coating remain on 91.4% of initial capacity first, and the material that does not coat only 46.9% illustrate coating AlF
3The cycle life of back basis material under high magnification is greatly improved.
Embodiment 2
Accurately take by weighing 0.060g NH
4HF
2, the NH of preparation 0.005mol/L
4HF
2Solution.Take by weighing 3.0g basis material LiNi
1/3Co
1/3Mn
1/3O
2With 0.200g Al (NO
3)
312H
2O puts into the beaker of 500ml, adds the redistilled water of 100ml, is placed on and fully stirs 10min on the magnetic stirring apparatus.Low whipping speed is 300r/min, and temperature is under 45 ℃, with buret with the rate of titration of 1.5ml/min to basis material and Al (NO
3)
312H
2Drip the NH of preparation in the mixed liquor of O
4HF
2Solution (the F/Al mol ratio is about 4.5).Other step is with embodiment 1.
Accurately take by weighing 0.079g NH
4HF
2, the NH of preparation 0.005mol/L
4HF
2Solution.Take by weighing 3.0g basis material LiNi
1/3Co
1/3Mn
1/3O
2With 0.200g Al (NO
3)
312H
2O puts into the beaker of 500ml, adds the redistilled water of 100ml, is placed on and fully stirs 10min on the magnetic stirring apparatus.Low whipping speed is 300r/min, and temperature is under 45 ℃, with buret with the rate of titration of 1.5ml/min to basis material and Al (NO
3)
312H
2Drip the NH of preparation in the mixed liquor of O
4HF
2Solution (the F/Al mol ratio is about 6.0).Other step is with embodiment 1.
Claims (5)
1. a method for coating that effectively improves the porous clad material of rate performance of lithium nickel cobalt manganese oxygen is characterized in that, may further comprise the steps: (1) presses A1/LiNi
1/3Co
1/2Mn
1/2O
2Mol ratio is the soluble aluminum salting liquid of 0.5%～3.0% preparation homologue quality, joins positive electrode LiNi
1/3Co
1/3Mn
1/3O
2The aqueous solution in, stir mixing;
(2) by the F/Al mol ratio be 3～6, the ammonium hydrogen fluoride solution of preparation homologue quality splashes into ammonium hydrogen fluoride solution in (1) described solution, stirs, mixing finishes to reaction;
(3) behind the solution left standstill 2～5h with (2) step gained, through vacuum filtration, the precipitation that obtains after the drying, is put into the Muffle furnace roasting, and furnace atmosphere is argon gas (can also be nitrogen), and calcining heat is 200 ℃～650 ℃, obtains having coated porous Al F
3The active substances in cathode materials powder of book film.
2. a kind of effective method for coating that improves the porous clad material of rate performance of lithium nickel cobalt manganese oxygen according to claim 1 is characterized in that described F/Al mol ratio is 3.5～4.5.
3. a kind of effective method for coating that improves the porous clad material of rate performance of lithium nickel cobalt manganese oxygen according to claim 1 is characterized in that, (3) step, described roasting time was 1～8h.
4. a kind of effective method for coating that improves the porous clad material of rate performance of lithium nickel cobalt manganese oxygen according to claim 1 is characterized in that Al/LiNi
1/3Co
1/3Mn
1/3O
2Mol ratio is 1.5%.
5. a kind of effective method for coating that improves the porous clad material of rate performance of lithium nickel cobalt manganese oxygen according to claim 1, it is characterized in that described soluble aluminum salting liquid is a kind of in aluminum nitrate solution, aluminum sulfate solution, aluminium acetate solution, the liquor alumini chloridi.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100357466A CN100490226C (en) | 2007-09-14 | 2007-09-14 | Coating method of porous clad material for effectively improving rate performance of lithium nickel cobalt manganese oxygen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100357466A CN100490226C (en) | 2007-09-14 | 2007-09-14 | Coating method of porous clad material for effectively improving rate performance of lithium nickel cobalt manganese oxygen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101154727A true CN101154727A (en) | 2008-04-02 |
| CN100490226C CN100490226C (en) | 2009-05-20 |
Family
ID=39256249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100357466A Active CN100490226C (en) | 2007-09-14 | 2007-09-14 | Coating method of porous clad material for effectively improving rate performance of lithium nickel cobalt manganese oxygen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100490226C (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244239A (en) * | 2011-05-27 | 2011-11-16 | 湖南长远锂科有限公司 | Method for preparing nickel cobalt aluminum serving as cathodic material of lithium ion battery |
| CN102324512A (en) * | 2011-09-19 | 2012-01-18 | 奇瑞汽车股份有限公司 | Surface-coated high voltage anode material LiNi0.5Mn1.5O4 and preparation method thereof |
| CN102593445A (en) * | 2012-03-15 | 2012-07-18 | 湖南杉杉户田新材料有限公司 | Aluminum clad manganese-base laminated composite lithium ion battery cathode material and preparation method thereof |
| CN102642855A (en) * | 2012-05-21 | 2012-08-22 | 湖南科技学院 | Preparation method of villiform aluminum fluoride |
| CN102738459A (en) * | 2012-07-17 | 2012-10-17 | 中国电子科技集团公司第十八研究所 | Surface fluoridation treatment method for positive pole material of manganese-based lithium ion battery |
| CN103094553A (en) * | 2013-01-12 | 2013-05-08 | 上海大学 | Method for modifying surface of anode material for lithium ion battery |
| CN103618084A (en) * | 2013-11-21 | 2014-03-05 | 刘铁建 | Mixed positive material of lithium-ion power battery |
| CN103650219A (en) * | 2011-06-24 | 2014-03-19 | 旭硝子株式会社 | Method for producing positive electrode active material for lithium-ion rechargeable batteries, positive electrode for lithium-ion rechargeable batteries, and lithium-ion rechargeable battery |
| CN103959543A (en) * | 2011-11-16 | 2014-07-30 | 丰田自动车株式会社 | Lithium ion secondary battery and method for manufacturing same |
| CN103996849A (en) * | 2014-05-16 | 2014-08-20 | 江苏华东锂电技术研究院有限公司 | Preparation method of lithium ion battery positive pole active material |
| CN104953112A (en) * | 2015-07-17 | 2015-09-30 | 诸暨帕瓦新能源有限公司 | Preparing method for porous spherical lithium ion battery material precursor coated with AlF3 |
| CN105161686A (en) * | 2015-09-15 | 2015-12-16 | 华南师范大学 | Double-coated manganese-base layered lithium-rich material and preparation method thereof |
| CN105958017A (en) * | 2016-05-10 | 2016-09-21 | 山东玉皇新能源科技有限公司 | Preparation method for aluminum-fluoride-coated lithium nickel cobalt manganate positive electrode material |
| CN108288694A (en) * | 2017-12-30 | 2018-07-17 | 宁夏科捷锂电池股份有限公司 | A kind of Mg2+Adulterate AlF3Coat the preparation method of tertiary cathode material |
| CN109716564A (en) * | 2016-09-21 | 2019-05-03 | 巴斯夫户田电池材料有限公司 | Positive active material and its manufacturing method and non-aqueous electrolyte secondary battery |
| CN111682170A (en) * | 2020-05-20 | 2020-09-18 | 广东邦普循环科技有限公司 | Single crystal ternary cathode material and preparation method and application thereof |
| CN107394154B (en) * | 2017-07-18 | 2020-12-22 | 郭芬 | Method for improving performance of ternary cathode material |
-
2007
- 2007-09-14 CN CNB2007100357466A patent/CN100490226C/en active Active
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244239B (en) * | 2011-05-27 | 2013-11-27 | 湖南长远锂科有限公司 | Method for preparing nickel cobalt aluminum serving as cathodic material of lithium ion battery |
| CN102244239A (en) * | 2011-05-27 | 2011-11-16 | 湖南长远锂科有限公司 | Method for preparing nickel cobalt aluminum serving as cathodic material of lithium ion battery |
| US9444099B2 (en) | 2011-06-24 | 2016-09-13 | Asahi Glass Company, Limited | Process for producing cathode active material for lithium ion secondary battery, cathode for lithium ion secondary battery, and lithium ion secondary battery |
| CN103650219A (en) * | 2011-06-24 | 2014-03-19 | 旭硝子株式会社 | Method for producing positive electrode active material for lithium-ion rechargeable batteries, positive electrode for lithium-ion rechargeable batteries, and lithium-ion rechargeable battery |
| CN102324512A (en) * | 2011-09-19 | 2012-01-18 | 奇瑞汽车股份有限公司 | Surface-coated high voltage anode material LiNi0.5Mn1.5O4 and preparation method thereof |
| CN103959543A (en) * | 2011-11-16 | 2014-07-30 | 丰田自动车株式会社 | Lithium ion secondary battery and method for manufacturing same |
| CN102593445A (en) * | 2012-03-15 | 2012-07-18 | 湖南杉杉户田新材料有限公司 | Aluminum clad manganese-base laminated composite lithium ion battery cathode material and preparation method thereof |
| CN102593445B (en) * | 2012-03-15 | 2014-12-24 | 湖南杉杉户田新材料有限公司 | Aluminum clad manganese-base laminated composite lithium ion battery cathode material and preparation method thereof |
| CN102642855A (en) * | 2012-05-21 | 2012-08-22 | 湖南科技学院 | Preparation method of villiform aluminum fluoride |
| CN102738459A (en) * | 2012-07-17 | 2012-10-17 | 中国电子科技集团公司第十八研究所 | Surface fluoridation treatment method for positive pole material of manganese-based lithium ion battery |
| CN103094553A (en) * | 2013-01-12 | 2013-05-08 | 上海大学 | Method for modifying surface of anode material for lithium ion battery |
| CN103618084A (en) * | 2013-11-21 | 2014-03-05 | 刘铁建 | Mixed positive material of lithium-ion power battery |
| CN103996849A (en) * | 2014-05-16 | 2014-08-20 | 江苏华东锂电技术研究院有限公司 | Preparation method of lithium ion battery positive pole active material |
| CN104953112A (en) * | 2015-07-17 | 2015-09-30 | 诸暨帕瓦新能源有限公司 | Preparing method for porous spherical lithium ion battery material precursor coated with AlF3 |
| CN104953112B (en) * | 2015-07-17 | 2017-06-27 | 诸暨帕瓦新能源有限公司 | The preparation method of the coated porous ball-shaped lithium-ion battery material precursors of AlF3 |
| CN105161686A (en) * | 2015-09-15 | 2015-12-16 | 华南师范大学 | Double-coated manganese-base layered lithium-rich material and preparation method thereof |
| CN105958017A (en) * | 2016-05-10 | 2016-09-21 | 山东玉皇新能源科技有限公司 | Preparation method for aluminum-fluoride-coated lithium nickel cobalt manganate positive electrode material |
| CN109716564A (en) * | 2016-09-21 | 2019-05-03 | 巴斯夫户田电池材料有限公司 | Positive active material and its manufacturing method and non-aqueous electrolyte secondary battery |
| CN109716564B (en) * | 2016-09-21 | 2022-09-09 | 巴斯夫户田电池材料有限公司 | Positive electrode active material, method for producing same, and nonaqueous electrolyte secondary battery |
| CN107394154B (en) * | 2017-07-18 | 2020-12-22 | 郭芬 | Method for improving performance of ternary cathode material |
| CN108288694A (en) * | 2017-12-30 | 2018-07-17 | 宁夏科捷锂电池股份有限公司 | A kind of Mg2+Adulterate AlF3Coat the preparation method of tertiary cathode material |
| CN111682170A (en) * | 2020-05-20 | 2020-09-18 | 广东邦普循环科技有限公司 | Single crystal ternary cathode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100490226C (en) | 2009-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100490226C (en) | Coating method of porous clad material for effectively improving rate performance of lithium nickel cobalt manganese oxygen | |
| CN113942990B (en) | Lithium iron manganese phosphate precursor, lithium iron manganese phosphate positive electrode material, preparation method of lithium iron manganese phosphate positive electrode material, electrode, and lithium ion battery | |
| Lu et al. | Cerium fluoride coated layered oxide Li1. 2Mn0. 54Ni0. 13Co0. 13O2 as cathode materials with improved electrochemical performance for lithium ion batteries | |
| CN109659542B (en) | High-voltage lithium cobalt oxide cathode material with core-shell structure and preparation method thereof | |
| CN110233247A (en) | Positive active material, positive pole piece and electrochemical energy storage device | |
| CN111261851B (en) | Ternary cathode material of lithium ion battery and preparation method thereof | |
| CN109437339A (en) | Nickelic quaternary positive electrode material precursor and nickelic quaternary positive electrode, preparation method and purposes | |
| CN110233259A (en) | Positive active material, positive pole piece and electrochemical energy storage device | |
| CN111115713B (en) | LaMnO3Coated lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN110492095B (en) | Tin-doped lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN108598379A (en) | A kind of tungstate lithium cladding nickel cobalt aluminic acid lithium composite material and its preparation method and application | |
| CN110323432A (en) | A kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping and preparation method thereof | |
| CN109309229A (en) | A kind of nickelic quaternary positive electrode, the Preparation method and use of coating modification | |
| CN108987683A (en) | A kind of preparation method of carbon coating tertiary cathode material | |
| WO2018030199A1 (en) | Positive electrode active material for nonaqueous electrolyte secondary batteries and method for producing positive electrode active material for nonaqueous electrolyte secondary batteries | |
| JP7121219B1 (en) | Method for producing lithium metal composite oxide | |
| CN107200358A (en) | A kind of iron system CuFe for sodium-ion battery2O4The preparation method of material | |
| CN114883522A (en) | High-entropy-like multi-element layered transition metal oxide cathode material and preparation method and application thereof | |
| CN103887496B (en) | A kind of preparation method of high performance lithium ion battery anode material LiMBO3C composite material | |
| CN112299487B (en) | All-manganese or high-manganese-based lithium-rich layered cathode material with disordered cations in layer and preparation method thereof | |
| JP2018014208A (en) | Positive electrode active material for nonaqueous electrolyte secondary battery and method for manufacturing the same | |
| CN106067545A (en) | One sodium metaaluminate makees raw material cladding stratiform method for preparing anode material | |
| CN115732661A (en) | Positive active material and application thereof | |
| CN112928267A (en) | Composite lithium-rich cathode material and preparation method and application thereof | |
| CN110474046B (en) | Spinel-phase lithium manganate coated lithium-rich manganese cathode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHENZHEN CITY TIANJIAO TECHNOLOGY DEVELOPMENT CO., Free format text: FORMER OWNER: CENTRAL-SOUTH CHINA UNIV. Effective date: 20090814 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090814 Address after: Floor 2, building A28, Ben Kang Industrial Zone, Kwai Chung street, Longgang District, Shenzhen, Guangdong Patentee after: Shenzhen Tianjiao Technology Development Co.,Ltd. Address before: Hunan province Changsha Hexi Lushan Road No. 1 Institute of metallurgy Patentee before: Central South University |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20190506 Address after: 222200 No. 5 Pioneering Road, SME Park, Lingang Industrial Zone, Guanyun County, Lianyungang City, Jiangsu Province Patentee after: GUANYUN TIANJIAO TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 518119 2nd Floor, Building A28, Pengkang Industrial Zone, Kuiyong Street, Longgang District, Shenzhen Patentee before: Shenzhen Tianjiao Technology Development Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220914 Address after: 276000 Yan'an Road 119, Linyi Economic and Technological Development Zone, Shandong Province Patentee after: Shandong Tianjiao new energy Co.,Ltd. Address before: 222200 No. 5 Pioneering Road, SME Park, Lingang Industrial Zone, Guanyun County, Lianyungang City, Jiangsu Province Patentee before: GUANYUN TIANJIAO TECHNOLOGY DEVELOPMENT Co.,Ltd. |
|
| TR01 | Transfer of patent right |