CN105130389A - Strong-alkali corrosion-resistant high-temperature-resistant container for cathode material of lithium battery, interface layer of container and preparation method for container - Google Patents
Strong-alkali corrosion-resistant high-temperature-resistant container for cathode material of lithium battery, interface layer of container and preparation method for container Download PDFInfo
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- CN105130389A CN105130389A CN201510531192.3A CN201510531192A CN105130389A CN 105130389 A CN105130389 A CN 105130389A CN 201510531192 A CN201510531192 A CN 201510531192A CN 105130389 A CN105130389 A CN 105130389A
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- interfacial layer
- oxide
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000005260 corrosion Methods 0.000 title claims abstract description 20
- 230000007797 corrosion Effects 0.000 title claims abstract description 19
- 239000003513 alkali Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010406 cathode material Substances 0.000 title abstract description 7
- 239000000835 fiber Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical class [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 5
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 4
- 239000010405 anode material Substances 0.000 claims description 28
- 230000003628 erosive effect Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052863 mullite Inorganic materials 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 238000010304 firing Methods 0.000 abstract description 7
- 239000002585 base Substances 0.000 abstract description 5
- 230000035939 shock Effects 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000696 magnetic material Substances 0.000 description 8
- 239000012611 container material Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000003245 working effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000013731 heat acclimation Effects 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of firing of cathode materials of lithium batteries and particularly relates to a strong-alkali corrosion-resistant high-temperature-resistant container for a cathode material of a lithium battery, an interface layer of the container and a preparation method for the container. The strong-alkali corrosion-resistant high-temperature-resistant interface layer comprises the following components in percentage by mass: 30-55% of aluminum oxide, 20-50% of silicon oxide, 0-15% of nickel oxide, 0-10% of zirconium oxide, 5-25% of magnesium oxide and 5-18% of lithium oxide. The strong-alkali corrosion-resistant high-temperature-resistant container for the cathode material of the lithium battery comprises a container main body and a strong-alkali corrosion-resistant high-temperature-resistant interface layer arranged on a working face of the container main body. The container provided by the invention has the advantages that 1, a strong-alkali corrosion-resistant material system is designed as the interface layer of the container and the cathode material of the lithium battery, so that high-temperature lithium-corrosion resistance is realized; and 2, surface coating modified aluminum silicate ceramic fiber is introduced into the high-temperature container base body material, so that the fired container base body has a network staggered structure, and therefore, the thermal shock resistance of the high-temperature container is improved, and the containers do not crack as the service life reaches 15-20 times.
Description
Technical field
The present invention relates to anode material of lithium battery burning techniques field, be specifically related to the anti-alkali corrosion high-temperature resistant container of a kind of anode material of lithium battery, its interfacial layer and preparation method thereof.
Background technology
Along with lithium cell is to the development in high-performance power battery direction, require more and more higher to the kind (as high-density lithium cobalt oxide system, nickelic ternary system) of anode material of lithium battery and manufacturing conditions (as firing temperature improves), accordingly higher requirement be it is also proposed to the performance of burning till anode material of lithium battery container.Container material not only can not pollute positive electrode material, also should have the performances such as good erosion-resisting characteristics, thermostability and atmosphere adaptability.Present widely used clayey and High-Alumina container due in use occur peeling, fall slag, pollute and burn till the development that the problems such as material seriously restrict anode material of lithium battery.Therefore, a kind of novel lithium battery positive electrode material high-performance container material is developed significant
Container used in anode material of lithium battery building-up process is generally corundum, mullite, quartzose and cordierite high-temperature resistant container.Wherein cordierite and corundum container is maximum.But can decompose in building-up process because synthesis anode material of lithium battery is raw materials used and produce seepage force and the strong Lithium Oxide 98min of reactive behavior corrodes high-temperature resistant container, the product of corrosion reaction simultaneously can pollute positive electrode material, cause impurity in positive electrode material, magnetic material content exceeds standard, reduce specific storage and the energy density of positive electrode material, finally cause the work-ing life of lithium cell, consistence and security to reduce; On the other hand, when container material cools fast after high temperature, along with the increase of access times, container easily cracks, and the thermal shock resistance of container is damaged, and the work-ing life of high-temperature resistant container can reduce greatly.
According to statistics, time at present for cobalt acid lithium high―temperature nuclei, even if temperature is at 1000 DEG C, domestic elevated temperature vessel only has about 5 ~ 6 times mean life, external imported product can remain between 15 ~ 20 times substantially, but the price of imported product is more than domestic several times, be difficult to meet domestic anode material of lithium battery producer to the requirement of elevated temperature vessel technico-economical comparison.
In sum, current domestic anode material of lithium battery burns till with the not resistance to alkali corrosion of ubiquity high temperature in elevated temperature vessel use procedure, easy cracking, work-ing life is short, magnetic material content exceeds standard, the problems such as easy pollution positive electrode material, be difficult to the making requirement meeting novel lithium battery positive electrode material, the development of serious restriction anode material of lithium battery, therefore, pin of the present invention is from these problems from high-temperature resistant container material system, the aspect such as structure design and manufacture craft is innovated, develop and there is the corrosion of anti-strong basicity, the high-temperature resistant container of high thermal shock resistance, meet novel lithium battery positive electrode material and burn till service requirements.
Summary of the invention
For solving the deficiencies in the prior art, the invention provides a kind of anode material of lithium battery high-performance high-temperature resistant container, its interfacial layer and preparation method thereof.
A kind of anti-highly basic high temperature erosion interfacial layer, comprises each composition of following mass percentage: aluminum oxide 30 ~ 55%, silicon oxide 20 ~ 50%, nickel oxide 0 ~ 15%, zirconium white 0 ~ 10%, magnesium oxide 5 ~ 25%, Lithium Oxide 98min 5 ~ 18%.
Preferably, the content of nickel oxide is greater than zero.
Preferred, zirconic content is greater than zero.
Present invention also offers a kind of preparation method of anti-highly basic high temperature erosion interfacial layer, comprise the following steps:
1) by aluminum chloride, lithium hydroxide, nickelous nitrate, zirconium nitrate, citric acid, deionized water by weight: 5 ~ 15:2 ~ 10:0 ~ 10:0 ~ 10:1 ~ 3:55 ~ 90 weigh, be placed in the container with whipping appts, and be heated between 45 ~ 60 DEG C, continue to stir insulation reaction 1 ~ 5 hour, obtain mixed solution system.
2) with ammoniacal liquor (concentration is 8 ~ 12%wt) by step 1) the mixed solution system pH that obtains is adjusted to 9 ~ 13, continue stirring 0.5 ~ 1 hour, then continue heating direct and evaporate completely to moisture, obtain jel product.
3) by step 2) jel product that obtains is placed in retort furnace 450 ~ 550 DEG C calcining and obtains powdered product after 0.5 ~ 1 hour.
4) by step 3) powdered product that obtains and triphane (granularity is 100 ~ 200 orders) by weight: 70 ~ 95:5 ~ 20 weigh, and are placed in mixing equipment and mix, and can obtain anti-highly basic high temperature erosion interfacial layer compound.
Preferably, step 1) in, the addition of nickelous nitrate is greater than zero.
Preferred, step 1) in, the addition of zirconium nitrate is greater than zero.
Present invention also offers the anti-strong basicity corrosion high-temperature resistant container of a kind of anode material of lithium battery, comprise container body and be arranged on the interfacial layer on described container body working face, described interfacial layer is selected from the arbitrary described anti-highly basic high temperature erosion interfacial layer of claims 1 to 3.
Preferably, described container body comprises each composition of following mass percentage: trichroite 5 ~ 50%, mullite 5% ~ 40%, aluminum oxide 2 ~ 20%, kaolin 10% ~ 35%, silicon-dioxide 3 ~ 15%, aluminum silicate fiber 5 ~ 20%
Provided by the present invention, for anode material of lithium battery cracking in elevated temperature vessel use procedure and corrosion two large problems, by the innovative design of material system and the advance of preparation technology, achieve the high-performance of novel lithium battery positive electrode material elevated temperature vessel and the perfect adaptation of economy, have the following advantages:
1, design there is the interfacial layer of erosion resistant material system as container and anode material of lithium battery, realize the anti-lithium of high temperature and corrode;
2, introduce surface coating modification alumina-silicate ceramic fibre in elevated temperature vessel body material, realize, after container matrix is burnt till, there is the alternizer structure of network, thus improve elevated temperature vessel thermal shock resistance, realize not ftractureing for 15 ~ 20 times work-ing life.
Relative to prior art, technical superiority of the present invention is embodied in:
1) the anti-alkali corrosion high-temperature resistant container of anode material of lithium battery has higher working temperature, anode material of lithium battery can be met and burn till demand up to 1300 DEG C, under the hot conditions of 900 ~ 1300 DEG C, anti-alkali corrosion elevated temperature vessel service life cycle can reach 15 ~ 20 times.
2) the anode material of lithium battery anti-highly basic high temperature erosion interfacial layer physics of anti-alkali corrosion high-temperature resistant container and stable chemical nature, impurity can not be introduced in anode material of lithium battery, especially the introducing of Magnetic Materials impurity has been stopped, for the anode material of lithium battery of production high-quality provides strong guarantee.
Accompanying drawing explanation
Fig. 1 is the fabrication processing figure of anode material of lithium battery high-performance high-temperature resistant container provided by the present invention.
Embodiment
Be described principle of the present invention and feature below in conjunction with accompanying drawing, illustrated embodiment, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment
1, container carrier batching
Container carrier composition is: trichroite (granularity is 16 order ~ 100 orders), mullite (granularity is 8 order ~ 40 orders), aluminum oxide grain size is (150 ~ 300 order), kaolin (granularity is 120 order ~ 300 orders), silicon-dioxide (20 order ~ 100 order), aluminum silicate fiber (mean fibre length: 1.0 ~ 3.5mm average fibre diameter: 3.0 ~ 8.0 μm), each weight percentages of components is: trichroite 5 ~ 50%, mullite 5% ~ 40%, aluminum oxide 2 ~ 20%, kaolin 10% ~ 35%, silicon-dioxide 3 ~ 15%, aluminum silicate fiber 5 ~ 20%.
2, aluminum silicate fiber surface coating modification
The introducing of aluminum silicate fiber is to make elevated temperature vessel carrier finally form the alternizer sintered compact of microcosmos network, but front summary ensures that aluminum silicate fiber will form good distribution with other component particles material, therefore needs to carry out surface coating modification to fiber.Concrete technology coating modifying is as follows:
(1) selected coating modification agent is one or more mixing wherein of oleic acid, linolenic acid, stearic acid, palmitinic acid;
(2) aluminum silicate fiber and coating modification agent are by weight: 98 ~ 99.5%:0.5 ~ 2% weighing, are placed in horizontal ball mill and carry out mix grinding, and rotating speed is 10 ~ 70 revs/min, and the mix grinding time is 0.5 ~ 10 hour.
3, prepare the matrix material with anti-lithium corrosive property in conjunction with wet chemistry method and solid phase method, materials chemistry consists of aluminum oxide 30-55%, silicon oxide 20-50%, nickel oxide 0-15%, zirconium white 0 ~ 10%, magnesium oxide 5-25%, Lithium Oxide 98min 5-18%.Concrete preparation process is as follows:
(1) aluminum chloride, lithium hydroxide, nickelous nitrate, zirconium nitrate, citric acid, deionized water are by weight: 5 ~ 15%:2 ~ 10%:0 ~ 10%:0 ~ 10%:1 ~ 3%:55 ~ 90%, raw materials weighing, be placed in the container with whipping appts, and be heated between 45 ~ 60 DEG C, continue to stir insulation reaction 1 ~ 5 hour;
(2) with ammoniacal liquor (concentration is 10%wt), above-mentioned mixed solution system PH is adjusted to 9 ~ 13, continues stirring 0.5 ~ 1 hour, then continue heating direct and evaporate completely to moisture, obtain jel product;
(3) jel product that above-mentioned steps obtains is placed in retort furnace 500 DEG C calcining and obtains powdered product after 0.5 ~ 1 hour;
(4) by powdered product in step (3) and triphane (granularity is 100 ~ 200 orders) by weight: 70 ~ 95%:5 ~ 20% weighs, and be placed in mixing equipment and mix, can obtain and there is anti-lithium corrosive property interfacial layer compound.
4, mix
By step 1 proportion scale, powder and water are carried out mix and blend in dedicated mixer, stirring velocity is 30 ~ 150 revs/min, and churning time is 10 ~ 30 minutes;
5, carrier blank forming
Suppress container carrier base substrate by mixing material Special purpose pressing machine in step 4, forming pressure is 10 tons ~ 200 tons, 1 ~ 5 minute dwell time;
6, laminate shaping
By in step 3 preparation interlayer materials material distributing machine or be manually evenly distributed on bottom container carrier base substrate, 0.1mm ~ 3mm, control press pressure 10 ~ 100 tons, 0.5 ~ 5 minute dwell time, carrier base substrate directly laminates interface material;
7, burn till
Novel lithium battery positive electrode material high-performance high-temperature resistant container is burnt till by certain calcining system.(sintering temperature is 1250 DEG C ~ 1500 DEG C, and soaking time is 1 ~ 5 hour, and temperature rise rate is 1 DEG C ~ 10 DEG C/min).
Effect example
Utilize the technology of the present invention, make elevated temperature vessel by domestic current largest anode material of lithium battery producer requirement specification 320mm × 320mm × 100mm, and carry out performance index contrast with current domestic best level and Japanese imported product.
Work-ing life comparative illustration: carry out identical simultaneous test respectively by same producer, same time, same heat.Often organize each random selecting of every class 5, container in use ftractures or corrodes after any one situation occurs, namely represents this container rejection ("-" represents this situation and also do not occur, corrode or the another kind of situation that ftractures occurs).
Container introduces impurity comparative illustration to positive electrode material: contrast the situation of judgement container to positive electrode material introducing impurity by burning till iron level and magnetic material content in positive electrode material under the same terms, the mensuration of iron level is measured by the basic skills of iron level in aas determination solids.Magnetic medium measurement method and step are: (1) by positive electrode material ultrasonic disperse in a solvent, then adds polymer overmold magnet, ultrasonic absorption magnetic substance, obtain the polymer overmold magnet being adsorbed with magnetic substance; (2) the polymer overmold magnet being adsorbed with magnetic substance is carried out ultrasonic cleaning; (3) dissolve the polymer overmold magnet being adsorbed with magnetic substance after cleaning with nitric acid-hydrochloric acid mixed solution, obtain lysate; (4) magnetic material content in solution is measured with icp ms.
Concrete correlation data is as follows:
Table 1 certain 8 days factory's moons in year testing data contrast domestic
Remarks: No. 1 stove high-density lithium cobalt oxide synthesis
Be more than the firing test Data Comparison of Hunan factory high-density lithium cobalt oxide, its firing temperature is 1090 DEG C, data as can be seen from table 1, and product of the present invention can reach the service life cycle close to 20 times substantially, is on close level with Japanese import.In the positive electrode material that inventive container burns till, iron level can control within 50pp substantially, and magnetic material content, within 50ppb, is significantly better than domestic and Japanese imported product, provides strong guarantee for meeting the production of ultralow magnetic material content anode material of lithium battery.
Table 2 certain 10 days factory's moons in year testing data contrast domestic
Remarks: No. 4 nickelic tertiary cathode material synthesis of stove
It is more than Hunan factory tertiary cathode material firing test Data Comparison, its firing temperature is 980 DEG C, as can be seen from the table, the present invention recycles number of times substantially close to 20 times, in the corresponding positive electrode material burnt till, iron level can be controlled in 50ppm once in addition, and magnetic material content is lower than 50ppb, and overall target is all better than Japanese import level, what can meet novel tertiary anode material of lithium battery burns till requirement, ensures the serviceability that positive electrode material is good.
Elevated temperature vessel of the present invention is performance under comparatively elevated operating temperature
Table 3 burns till anode material of lithium battery laboratory correlation data at 1250 DEG C
By table 3 data declaration elevated temperature vessel of the present invention when anode material of lithium battery firing temperature is up to 1250 DEG C, still there is strong anti-alkali corrosion, good thermal shock performance, Comprehensive service life remains on about 15 times substantially, shows good heat acclimation performance.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. an anti-highly basic high temperature erosion interfacial layer, it is characterized in that, comprise each composition of following mass percentage: aluminum oxide 30 ~ 55%, silicon oxide 20 ~ 50%, nickel oxide 0 ~ 15%, zirconium white 0 ~ 10%, magnesium oxide 5 ~ 25%, Lithium Oxide 98min 5 ~ 18%.
2. anti-highly basic high temperature erosion interfacial layer according to claim 1, is characterized in that: the content of nickel oxide is greater than zero.
3. anti-highly basic high temperature erosion interfacial layer according to claim 1 and 2, is characterized in that: zirconic content is greater than zero.
4. a preparation method for anti-highly basic high temperature erosion interfacial layer, is characterized in that, comprise the following steps:
1) by aluminum chloride, lithium hydroxide, nickelous nitrate, zirconium nitrate, citric acid, deionized water by weight: 5 ~ 15:2 ~ 10:0 ~ 10:0 ~ 10:1 ~ 3:55 ~ 90 weigh, be placed in the container with whipping appts, and be heated between 45 ~ 60 DEG C, continue to stir insulation reaction 1 ~ 5 hour, obtain mixed solution system;
2) with ammoniacal liquor by step 1) the mixed solution system pH that obtains is adjusted to 9 ~ 13, continue stirring 0.5 ~ 1 hour, then continue heating direct and evaporate completely to moisture, obtain jel product;
3) by step 2) jel product that obtains is placed in retort furnace 450 ~ 550 DEG C calcining and obtains powdered product after 0.5 ~ 1 hour;
4) by step 3) powdered product that obtains and triphane by weight: 70 ~ 95:5 ~ 20 weigh, and are placed in mixing equipment and mix, and can obtain anti-highly basic high temperature erosion interfacial layer compound.
5. the preparation method of anti-highly basic high temperature erosion interfacial layer according to claim 4, is characterized in that, step 1) in, the addition of nickelous nitrate is greater than zero.
6. the preparation method of the anti-highly basic high temperature erosion interfacial layer according to claim 4 or 5, is characterized in that, step 1) in, the addition of zirconium nitrate is greater than zero.
7. the anti-alkali corrosion high-temperature resistant container of anode material of lithium battery, comprise container body and be arranged on the interfacial layer on described container body working face, it is characterized in that: described interfacial layer is selected from the arbitrary described anti-highly basic high temperature erosion interfacial layer of claims 1 to 3.
8. the anti-alkali corrosion high-temperature resistant container of anode material of lithium battery according to claim 7, it is characterized in that, described container body comprises each composition of following mass percentage: trichroite 5 ~ 50%, mullite 5% ~ 40%, aluminum oxide 2 ~ 20%, kaolin 10% ~ 35%, silicon-dioxide 3 ~ 15%, aluminum silicate fiber 5 ~ 20%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111233447A (en) * | 2020-01-16 | 2020-06-05 | 江苏润鸿高温窑具有限公司 | Preparation method of high-durability kiln furniture for positive electrode material of lithium-ion battery |
| CN115231908A (en) * | 2022-07-05 | 2022-10-25 | 洛阳欧斯特建材有限公司 | High-purity alumina brick for preparing lithium battery anode material kiln and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314549A (en) * | 2007-05-29 | 2008-12-03 | 卡塔罗尼安-阿拉贡斯矿业公司 | Metallic glaze composition |
| CN102001864A (en) * | 2010-12-04 | 2011-04-06 | 黄俊杰 | Heat-resistant porcelain glaze |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314549A (en) * | 2007-05-29 | 2008-12-03 | 卡塔罗尼安-阿拉贡斯矿业公司 | Metallic glaze composition |
| CN102001864A (en) * | 2010-12-04 | 2011-04-06 | 黄俊杰 | Heat-resistant porcelain glaze |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233447A (en) * | 2020-01-16 | 2020-06-05 | 江苏润鸿高温窑具有限公司 | Preparation method of high-durability kiln furniture for positive electrode material of lithium-ion battery |
| CN115231908A (en) * | 2022-07-05 | 2022-10-25 | 洛阳欧斯特建材有限公司 | High-purity alumina brick for preparing lithium battery anode material kiln and preparation method thereof |
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