CN102344168A - Method for synthesizing high tap density spinel material LiNi0.5Mn1.5O4 - Google Patents
Method for synthesizing high tap density spinel material LiNi0.5Mn1.5O4 Download PDFInfo
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- CN102344168A CN102344168A CN2011101866633A CN201110186663A CN102344168A CN 102344168 A CN102344168 A CN 102344168A CN 2011101866633 A CN2011101866633 A CN 2011101866633A CN 201110186663 A CN201110186663 A CN 201110186663A CN 102344168 A CN102344168 A CN 102344168A
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- lithium
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- nickel
- high tap
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 19
- 239000011029 spinel Substances 0.000 title claims abstract description 19
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 title claims abstract 3
- 239000000463 material Substances 0.000 title abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 239000000047 product Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 32
- 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 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 239000011572 manganese Substances 0.000 claims description 26
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 229910013716 LiNi Inorganic materials 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical class [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical class [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 12
- 239000012467 final product Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical class [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical class [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims description 2
- -1 carboxylic acid lithium salts Chemical class 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical class [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005118 spray pyrolysis Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 abstract description 14
- 238000003756 stirring Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 229960000583 acetic acid Drugs 0.000 description 12
- 239000012362 glacial acetic acid Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Chemical group 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Chemical group 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- SKHRSLLIVMEGOA-UHFFFAOYSA-N dilithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Li+].[Li+].[Ni++].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O SKHRSLLIVMEGOA-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- UGPIGYYLADCIFW-UHFFFAOYSA-N dioxido(dioxo)manganese;nickel(2+) Chemical compound [Ni+2].[O-][Mn]([O-])(=O)=O UGPIGYYLADCIFW-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
The invention discloses a method for synthesizing a high tap density spinel material LiNi0.5Mn1.5O4. The method is characterized by comprising the steps of: (1) dissolving a lithium salt, a nickel salt, a manganese salt and an additive in certain proportion in deionized water, stirring and heating the water so as to form a sol mixture; (2) presintering the sol at a specific temperature for a specific period of time, thus obtaining a primary product; (3) subjecting the primary product to high temperature formal sintering for a specific period of time under a specific temperature, thus obtaining an end product. The process of the invention has the characteristics of simple gel forming method, short production period, lower energy consumption, less hidden dangers in large scale production, and low production cost, etc. And the spinel-type nickel lithium manganate positive material prepared by the method of the invention has the advantages of high product purity, high tap density, uniform product particle and stable electrochemical performance.
Description
Technical field
The invention belongs to the synthetic field of inorganic functional material, be fit to the preparation of high tap density lithium ion battery 5V level positive electrode material.
Background technology
Generally the anode material for lithium-ion batteries of charge and discharge platform more than 4.5V is called the noble potential positive electrode material, or 5V level positive electrode material, according to present result of study, this type noble potential positive electrode material mainly contains spinel type LiM
xMn
2-xO
4(0≤x≤1, M is iron, copper, cobalt, nickel, chromium and consanguinity transition metal thereof) here, olivine-type LiMPO
4(M is cobalt, nickel, chromium and consanguinity transition metal thereof), and the material of other plurality of layers shape structure.Wherein, (chemical formula is: LiNi to have the spinel property nickel lithium manganate material of 4.7V voltage platform
0.5Mn
1.5O
4), no matter be all to be proved from Theoretical Calculation or from breadboard preparation research to have excellent application prospect, be a focus of present high-potential material exploitation.
High-potential material nickel lithium manganate with 5V level charge and discharge platform is suitable for the needs of high power battery because of higher more than 30% than traditional cobalt acid lithium voltage (3.7V).Through years of development, along with the development of high-potential material supporting technology (for example noble potential electrolytic solution), high-potential material nickel lithium manganate moves towards the practicability exploitation from technology of preparing, basic Electrochemical Properties etc. gradually.For example, " nickel lithium manganate-lithium titanate " battery of the Ohzuku of Osaka, Japan City University and the cooperation of SANYO electronics assembling capability retention of 90% in addition that under 2C, circulates after 2000 times; Korea S's LG chemistry has been manufactured experimently 600mAh's " nickel lithium manganate-graphite " soft-package battery; French CE A subordinate's liten company has manufactured experimently 2Ah's " nickel lithium manganate-graphite " soft-package battery; The ETVM company of Israel then with such " nickel lithium manganate-graphite " battery successful Application on telecontrolled aircraft.Others, the Daikin Industries of Japan has also been released the fluorine-containing electrolyte that can be used for the 4.7V voltage platform to the application requiring of noble potential nickel lithium manganate; U.S. Enerdel company is then just carrying out under the subsidy of USDOE and can be used for plug-in hybrid automobile-used " nickel lithium manganate-lithium titanate " battery research
At present; The industrialization development of noble potential anode material nickel lithium manganate has welcome important opportunity; Particularly under the fast-developing situation of national new forms of energy industry; To have the variety of problems that various anodal equivalent material occur now in practicality; And in the large-sized power field of batteries; Energy-storage battery fields etc. are to the security of battery material of new generation; Work-ing life; The harsh requirement that aspects such as cost propose; Noble potential nickel lithium manganate material is to be hopeful most to obtain the revolutionary lithium ion anode material of breaking through in lithium electricity industry, becomes the key player of new energy field.
Employing ethanol such as Yu Zuolong are that dispersion medium prepares nickel lithium manganate material (CN 101844817 A), and this patent described " sol-gel-self-propagating combustion " because will contain the combustion processes of a large amount of ethanol colloidal sols and possibly cause the combustion explosion potential safety hazard to limit its application in industrialized production through one.In addition, comprise that the liquid phase method of many pieces of bibliographical informations of above-mentioned patent prepares the often difficult tap density that improves product of route of nickel lithium manganate, this has also limited the application of prepared electrode materials in the actual battery production technique.
Summary of the invention
The method that the purpose of this invention is to provide a kind of low cost, be prone to mass-producing, safe being used to of industrial operation prepares high tap density 5V level anode material for lithium-ion batteries spinel type nickel lithium manganate,
Be used to prepare the method for high tap density 5V level anode material for lithium-ion batteries spinel type nickel lithium manganate: preparation of raw material is become colloidal sol, this colloidal sol is obtained final product through pre-burning, formal calcination processing.It is simple that this process has into a gluing method; With short production cycle; Characteristics such as energy consumption is low, potential safety hazard is few in the large-scale production, production cost is few, and, tap density high, product uniform particles high through the spinel type nickel manganate cathode material for lithium product purity of this method preparation, stable electrochemical property.
Below be narration about the present invention's " a kind of method for preparing high tap density 5V level anode material for lithium-ion batteries spinel type nickel lithium manganate ":
Preparing method of the present invention comprises following processing step:
the crude product at a specific temperature over a certain time after the final calcination temperature formal product.
According to technological line provided by the invention; It is characterized in that: the employing deionized water is a solvent; With lithium, nickel, manganic compound and relevant auxiliary agent is raw material; Form colloidal sol; Be implemented in the homodisperse on the molecular level; Drying, dehydration, low temperature presintering, high-temperature calcination through necessary finally form the good nickel lithium manganate product of chemical property.
According to technological line of the present invention, the lithium salts that is adopted comprises Quilonum Retard, lithium hydroxide, lithium nitrate, reaches the mixture of one or more several salt in the various carboxylic acid lithium salts such as lithium formate, lithium acetate; The nickel salt that is adopted comprises the mixture of one or both salt in nickelous nitrate, the nickelous acetate, and the nickelous nitrate, the nickelous acetate that are obtained through nitrification, acetic acid reaction by nickel raw materials such as metallic nickel, nickel hydroxide, nickelous carbonate, nickel oxide; The manganese salt that is adopted comprises the mixture of one or both salt in manganous nitrate, the manganous acetate,, and the manganous nitrate, the manganous acetate that obtain through nitrification, acetic acid reaction by nickel raw materials such as manganese metal, manganous hydroxide, manganous carbonate, manganese oxide; Wherein, the mol ratio of lithium salts, nickel salt and its lithium of manganese salt, nickel, manganese is: n
Li: n
Ni: n
Mn=1.95 ~ 2.2:1.0 ~ 1.1:3.0, top condition is n
Li: n
Ni: n
Mn=2.1: 1.05: 3.0.The auxiliary agent that is adopted comprises the mixture of one or more the two kinds of salt in Hydrocerol A, the urea, and the adjuvant used quality and the mass ratio of final product are m
Auxiliary agent: m
Product=1 ~ 3:2, top condition is m
Auxiliary agent: m
Product=1:1.
According to technological line of the present invention, the acquisition mode of elementary product be below a kind of in several modes: 1. directly heating pre-burning under specified temp of colloidal sol; 2. colloidal sol obtains dried powder through spraying drying, pre-burning under given conditions more earlier; 3. colloidal sol directly carries out spray pyrolysis under given conditions; The temperature limit of described colloidal sol pre-burning fixes between 300 ℃ ~ 600 ℃, and the pre-burning time is 0 ~ 6 hour.Top condition be 550 ℃ following 3 hours.
According to technological line of the present invention; The high-temperature calcination that the head product that obtains after the colloidal sol pre-burning must pass through under the specified conditions could finally obtain spinel type nickel lithium manganate; The temperature limit that is adopted fixes between 600 ℃ ~ 850 ℃; The pre-burning time is 3 ~ 24 hours, top condition be 800 ℃ following 12 hours.
The preparation method of lithium ion secondary battery anode material of the present invention compared with prior art has following advantage:
1. the present invention has realized the uniform mixing of reaction raw materials on molecular level through the mode that forms liquid phase colloidal sol;
2. the present invention has reduced the quantity of the needed Hydrocerol A of conventional gel method by coordination between contained metal ion of raw material self and the carboxyl, has reduced production cost;
3. the present invention is simple to operate, technology is easy to control, non-environmental-pollution;
4. the present invention adopts water to make solvent, in large-scale production, is difficult for causing security incident;
5. the product that obtains of the present invention is compared characteristics such as having the tap density height with the product that the common sol method obtains, and in lithium ion battery, uses processibility good, helps improving the energy density of battery.
Description of drawings
Fig. 1 is the LiNi that utilizes the present invention to prepare
0.5Mn
1.5O
4The crystal morphology figure of positive electrode material;
Fig. 2 is the LiNi that utilizes the present invention to prepare
0.5Mn
1.5O
4Charging and discharging curve behind positive electrode material and the metallic lithium composition CR2032 type button cell under 0.2C;
Fig. 3 is the LiNi that utilizes the present invention to prepare
0.5Mn
1.5O
4Charging and discharging curve behind positive electrode material and the metallic lithium composition CR2032 type button cell under 10C;
Fig. 4 is the LiNi that utilizes the present invention to prepare
0.5Mn
1.5O
4Cycle performance behind positive electrode material and the metallic lithium composition CR2032 type button cell under 2C.
Embodiment
Embodiment 1
With Quilonum Retard, nickelous nitrate, manganous acetate, Hydrocerol A, Glacial acetic acid is raw material, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is mixing in 1: 0.5: 1.5 (mol ratio, down together).Earlier Quilonum Retard is added the reaction of capacity Glacial acetic acid and form Lithium Acetate, join then in the nickel nitrate solution, again manganous acetate, Hydrocerol A are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 12 hours down for 3 hours, 750 ℃ through 350 ℃ of following pre-burnings, obtains final product, and tap density is 2.3g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 145mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 121mAh/g under the 10C condition, and the 2C capability retention after the circulation 800 times down is more than 88%.
Embodiment 2
With Quilonum Retard, nickelous nitrate, manganous acetate, Hydrocerol A, Glacial acetic acid is raw material, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is mixing in 1.05: 0.5: 1.5 (mol ratio, down together).Earlier Quilonum Retard is added the reaction of capacity Glacial acetic acid and form Lithium Acetate, join then in the nickel nitrate solution, again manganous acetate, Hydrocerol A are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 12 hours down for 1 hour, 800 ℃ through 450 ℃ of following pre-burnings, obtains final product, and tap density is 2.5g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 143mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 117mAh/g under the 10C condition, and the 2C capability retention after the circulation 100 times down is more than 90%.
Embodiment 3
With Quilonum Retard, nickelous nitrate, manganous acetate, Hydrocerol A, Glacial acetic acid is raw material, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is mixing in 1.: 0.52: 1.5 (mol ratio, down together).Earlier Quilonum Retard is added the reaction of capacity Glacial acetic acid and form Lithium Acetate, join then in the nickel nitrate solution, again manganous acetate, Hydrocerol A are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 3 hours down for 1 hour, 800 ℃ through 550 ℃ of following pre-burnings, obtains final product, and tap density is 2.38g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 146mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 119mAh/g under the 10C condition, and the 2C capability retention after the circulation 500 times down is more than 95%.
Embodiment 4
With lithium hydroxide, nickelous nitrate, manganous acetate, Hydrocerol A, Glacial acetic acid is raw material, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is mixing in 1: 0.5: 1.5 (mol ratio, down together).Earlier lithium hydroxide is added the reaction of capacity Glacial acetic acid and form Lithium Acetate, join then in the nickel nitrate solution, again manganous acetate, Hydrocerol A are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 12 hours down for 1 hour, 750 ℃ through 550 ℃ of following pre-burnings, obtains final product, and tap density is 2.3g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 144mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 117mAh/g under the 10C condition, and the 2C capability retention after the circulation 200 times down is more than 99%.
Embodiment 5
With Lithium Acetate, metallic nickel, manganous acetate, Hydrocerol A, nitric acid is raw material, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is mixing in 1: 0.5: 1.5 (mol ratio, down together).Earlier metallic nickel is added the capacity nitric acid reaction and form nickel nitrate solution, then Lithium Acetate is joined in the above-mentioned nickelous nitrate solution, again manganous acetate, Hydrocerol A are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 6 hours down for 2 hours, 750 ℃ through 500 ℃ of following pre-burnings, obtains final product, and tap density is 2.45g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 141mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 115mAh/g under the 10C condition, and the 2C capability retention after the circulation 200 times down is more than 97%.
Embodiment 6
With Lithium Acetate, nickelous carbonate, manganous acetate, Hydrocerol A, nitric acid is raw material, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is mixing in 1.1: 0.5: 1.5 (mol ratio, down together).Earlier nickelous carbonate is added the capacity nitric acid reaction and form nickel nitrate solution, then Lithium Acetate is joined in the above-mentioned nickelous nitrate solution, again manganous acetate, Hydrocerol A are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 18 hours down for 5 hours, 750 ℃ through 500 ℃ of following pre-burnings, obtains final product, and tap density is 2.6g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 139mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 112mAh/g under the 10C condition, and the 2C capability retention after the circulation 200 times down is 100%.
Embodiment 7
With Lithium Acetate, nickelous nitrate, manganous carbonate, urea, Glacial acetic acid is raw material, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is mixing in 1: 0.5: 1.5 (mol ratio, down together).Earlier manganous carbonate is added the reaction of capacity Glacial acetic acid and form manganese acetate solution, join in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation then with Lithium Acetate, nickelous nitrate, Hydrocerol A; The spray-dried formation powder of this colloidal sol is calcined this powder 18 hours down for 5 hours, 750 ℃ through 500 ℃ of following pre-burnings, obtains final product, and tap density is 2.65g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 139mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 112mAh/g under the 10C condition, and the 2C capability retention after the circulation 200 times down is 100%.
Claims (9)
1. synthetic high tap density spinel LiNi
0.5Mn
1.5O
4Method, it is characterized in that, may further comprise the steps and carry out:
2. synthetic high tap density spinel LiNi according to claim 1
0.5Mn
1.5O
4Method, it is characterized in that the lithium salts that is adopted comprises the mixture of one or more several salt in the various carboxylic acid lithium salts of Quilonum Retard, lithium hydroxide, lithium nitrate, lithium formate and lithium acetate.
3. synthetic high tap density spinel LiNi according to claim 1
0.5Mn
1.5O
4Method, it is characterized in that the nickel salt that is adopted comprises one or both the mixture in nickelous nitrate, the nickelous acetate, and the nickelous nitrate or the nickelous acetate that obtain through nitrification, acetic acid reaction by metallic nickel, nickel hydroxide, nickelous carbonate or nickel oxide.
4. synthetic high tap density spinel LiNi according to claim 1
0.5Mn
1.5O
4Method, it is characterized in that the manganese salt that is adopted comprises the mixture of one or both salt in manganous nitrate, the manganous acetate, and the manganous nitrate or the manganous acetate that obtain through nitrification, acetic acid reaction by manganese metal, manganous hydroxide, manganous carbonate or manganese oxide.
5. synthetic high tap density spinel LiNi according to claim 1
0.5Mn
1.5O
4Method, it is characterized in that the auxiliary agent that is adopted comprises the mixture of one or more the two kinds of salt in Hydrocerol A, the urea, the adjuvant used quality and the mass ratio of final product are 1 ~ 3:2.
6. synthetic high tap density spinel LiNi according to claim 1
0.5Mn
1.5O
4Method, it is characterized in that, step 2. in, the acquisition mode of said elementary product be below a kind of in several modes: the directly heating pre-burning under specified temp of a, colloidal sol; B, colloidal sol obtain dried powder through spraying drying, pre-burning under given conditions more earlier; C, colloidal sol directly carry out spray pyrolysis under given conditions.
7. synthetic high tap density spinel LiNi according to claim 1
0.5Mn
1.5O
4Method, it is characterized in that, be between 300 ℃ ~ 600 ℃ at the 2. said specified temp of step, specified time is 0 ~ 6 hour.
8. synthetic high tap density spinel LiNi according to claim 1
0.5Mn
1.5O
4Method, it is characterized in that, it is characterized in that, in step
In, described specified temp is limited between 600 ℃ ~ 850 ℃, and specified time is 3 ~ 24 hours.
9. synthetic high tap density spinel LiNi according to claim 1
0.5Mn
1.5O
4Method, it is characterized in that said specified proportion is that the mol ratio of lithium salts, nickel salt and its lithium of manganese salt of being adopted, nickel, manganese is: n
Li: n
Ni: n
Mn=1.95 ~ 2.2:1.0 ~ 1.1:3.0.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102800856A (en) * | 2012-08-31 | 2012-11-28 | 株洲天地龙电源科技有限公司 | Preparation method of manganic acid-nickel-lithium positive electrode with high specific energy and high power |
| CN102903897A (en) * | 2012-07-20 | 2013-01-30 | 合肥国轩高科动力能源有限公司 | Method for preparing nickel lithium manganate having spinel structure by static mixer type reactor |
| CN111018005A (en) * | 2019-12-06 | 2020-04-17 | 贵州大龙汇成新材料有限公司 | Spinel type lithium nickel manganese oxide material and preparation method thereof |
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| JP2011105565A (en) * | 2009-11-19 | 2011-06-02 | Tosoh Corp | Lithium manganate compound replaced by different metal and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102903897A (en) * | 2012-07-20 | 2013-01-30 | 合肥国轩高科动力能源有限公司 | Method for preparing nickel lithium manganate having spinel structure by static mixer type reactor |
| CN102800856A (en) * | 2012-08-31 | 2012-11-28 | 株洲天地龙电源科技有限公司 | Preparation method of manganic acid-nickel-lithium positive electrode with high specific energy and high power |
| CN111018005A (en) * | 2019-12-06 | 2020-04-17 | 贵州大龙汇成新材料有限公司 | Spinel type lithium nickel manganese oxide material and preparation method thereof |
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