CN103000879B - Preparation method of spinel type lithium-nickel-manganese oxide with one-dimensional porous structure - Google Patents
Preparation method of spinel type lithium-nickel-manganese oxide with one-dimensional porous structure Download PDFInfo
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- CN103000879B CN103000879B CN201210555361.3A CN201210555361A CN103000879B CN 103000879 B CN103000879 B CN 103000879B CN 201210555361 A CN201210555361 A CN 201210555361A CN 103000879 B CN103000879 B CN 103000879B
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Abstract
The invention relates to a preparation method of a spinel type lithium-nickel-manganese oxide with a one-dimensional porous structure, which comprises the following steps of: mixing a manganese salt solution with an oxalic acid or ammonium oxalate solution, and stirring for reaction; separating, depositing, and drying to obtain a manganous oxalate micron rod with a one-dimensional structure; and roasting the manganous oxalate micron rod at high temperature in the presence of air or oxygen, then uniformly mixing with a lithium source and a nickel source, and finally roasting the obtained mixture at high temperature to prepare the spinel type lithium-nickel-manganese oxide with the one-dimensional porous structure. The spinel type lithium-nickel-manganese oxide with the one-dimensional porous structure, which is disclosed by the invention, shows the excellent high-current discharge property due to less inside granule composition and larger specific area, enhances the endurance degree of a material on the volume change of the process of taking off or embedding lithium through the inside unique microstructure, effectively enhances the cycling stability of the material and is an ideal electrode material; and the preparation method disclosed by the invention is simple in process, easy to implement and conductive to popularization and application.
Description
Technical field
The present invention relates to the preparation of anode active material of lithium ion battery, particularly a kind of preparation method with the spinel-type Li-Ni-Mn-O of one dimension loose structure.
Background technology
Lithium ion battery has that operating voltage is high, energy density is large, have extended cycle life, operating temperature range is wide and the advantage such as safe memory-less effect, be the power supply that most consumption electronic product adopts, be also the very promising electrical source of power used for electric vehicle of one simultaneously.Lithium ion battery is primarily of positive pole, negative pole, barrier film and electrolyte four part composition, and usual positive pole is one of the key factor determining performance of lithium ion battery.The positive electrode that the lithium ion battery of Current commercial adopts is cobalt acid lithium, but its price, environment and safety problem limit its application in electrokinetic cell.Therefore cheap, the environmental friendliness of development cost and safe and reliable substitution material become the main target of anode material for lithium-ion batteries development.LiMn2O4 has spinel structure, its good stability, price are low, environment-protecting asepsis and good heavy current, it is a kind of positive electrode having very much application prospect, see O.K.Park, Y.Cho, S.Lee, et al.Who will drive electric vehicles, olivine or spinel Energy Environ.Sci., 2011,4:1621.Spinel-type Li-Ni-Mn-O is replaced by the part manganese nickel in LiMn2O4, its structure and LiMn2O4 similar, there is good stability and good heavy-current discharge performance, its voltage platform exceeds about 0.7V than LiMn2O4 simultaneously, therefore its power density and energy density are higher than LiMn2O4, are also a kind of positive electrodes having using value, see J.B.Goodenough and Y.Kim.Challenges for Rechargeable Li Batteries.Chem.Mater., 2009,22:587.
At present, the subject matter that LiMn2O4 faces in commercial applications is the decline of its capacity in charge and discharge process.Manganese in LiMn2O4 is with Mn
3+and Mn
4+form exists, wherein Mn
3+disproportionation is decomposed, phase transformation in the change in volume that causes of Jahn-Teller effect and removal lithium embedded process is the main cause causing its inducing capacity fading, see L.Xiong, Y.Xu, and T.Tao.Excellent stability of spinel LiMn2O4-basedcomposites for lithium ion batteries.J.Mater.Chem., 2012, DOI:10.1039/c2jm34717b.In Li-Ni-Mn-O, nearly all manganese is all with Mn
4+form exists, and at utmost reduces Mn
3+disproportionation decompose and Jahn-Teller effect, but its capacity still has obvious decline in charge and discharge process, this may be caused by the phase transformation in the side reaction of electrolyte and removal lithium embedded process.In addition, in order to meet the rigors of electrokinetic cell to positive electrode heavy-current discharge performance, the multiplying power discharging property of this bi-material need further reinforcement.Therefore, be very important to improve its cyclical stability and to strengthen its multiplying power discharging property by the structure of designing material and pattern.
The electrode material with one dimension micro-nano structure due to owing to comprising effective one dimension electric transmission path and shorter ion diffuse path, and shows superior chemical property.The electrode material with loose structure then can cushion structural strain in charge and discharge process, and loose structure can improve the contact area of active material and electrolyte, thus presents good cycle performance and high rate performance.Predict thus, have the advantage that a peacekeeping porous micro-nano structure material probably has these two kinds of structures simultaneously, the internal microstructure of its uniqueness can bring outstanding chemical property simultaneously.
Summary of the invention
The object of the invention is to for the problems referred to above, a kind of preparation method with the spinel-type Li-Ni-Mn-O of one dimension loose structure is proposed, the method is precursor with manganese oxalate, the solid phase insertion reaction kept by pattern prepares the spinel-type Li-Ni-Mn-O with one dimension loose structure, gained spinel-type Li-Ni-Mn-O is used as anode material of lithium battery, shows good cyclical stability and excellent heavy-current discharge performance.
Technical scheme of the present invention:
Have a preparation method for the spinel-type Li-Ni-Mn-O of one dimension loose structure, step is as follows:
1) preparation of the manganese oxalate micron bar of one-dimentional structure
Mixed with oxalic acid or ammonium oxalate solution by manganese salt solution and stirring reaction 20 minutes, precipitation and separation is also dry, and namely obtain the manganese oxalate micron bar of one-dimentional structure, its diameter is 0.2-3 μm, fineness ratio is 1:2-100;
2) preparation of spinel-type Li-Ni-Mn-O
By the above-mentioned manganese oxalate micron bar with one-dimentional structure in the presence of air or oxygen at 300-600 DEG C of roasting 2-15 hour, then mix with lithium source and nickel source, finally by gained mixture 300-900 DEG C of roasting 6-34 hour under air or oxygen atmosphere, prepare spinel-type Li-Ni-Mn-O, it has one dimension loose structure, diameter is 0.2-3 μm, fineness ratio is 1:2-20, average pore size is 10-20nm, and specific area is 4-7m
2/ g.
Described manganese salt is manganese chloride, manganese sulfate, manganese nitrate or manganese acetate, and the concentration of manganese salt solution is 0.05-1.5 mol/L; The concentration of oxalic acid or ammonium oxalate solution is 0.05-1.5 mol/L; Manganese salt solution and oxalic acid or ammonium oxalate solution volume ratio are 1:1-8.
Described lithium source is lithium hydroxide, lithium nitrate or lithium acetate, and nickel source is nickel acetate, nickel nitrate, nickel chloride or nickelous sulfate, and the mol ratio of the lithium in the manganese in manganese oxalate micron bar, lithium source and the nickel in nickel source is 1.5:1-1.05:0.5.
There is described in a kind of the application of the spinel-type Li-Ni-Mn-O of one dimension loose structure, for the preparation of lithium battery anode, described lithium battery comprises positive pole, lithium anode, barrier film and electrolyte, positive pole is by electrode material, conductive agent and binding agent composition, wherein electrode material comprises one dimension porous spinelle type Li-Ni-Mn-O, conductive agent is carbon nano-fiber, electrically conductive graphite, acetylene black, the mixture of one or more arbitrary proportions in Super P, binding agent is polytetrafluoroethylene or Kynoar, the mass percent of conductive agent and binding agent is respectively 20%-5%, 10%-5%, spinel-type Li-Ni-Mn-O is surplus, described barrier film is three layers of barrier film that polyethylene or polypropylene are formed, described electrolyte is the mixture of one or more arbitrary proportions of ethyl carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC).
Advantage of the present invention is: have the spinel-type Li-Ni-Mn-O of one dimension loose structure owing to having less internal particle composition and larger specific area, it is made to show excellent heavy-current discharge performance, and its inner unique microstructure improves material to the change in volume tolerance in removal lithium embedded process, effectively improve the cyclical stability of material, is a kind of desirable electrode material; This preparation method's technique is simple, easy to implement, is conducive to applying.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of manganese oxalate micron bar.
Fig. 2 is the scanning electron microscope (SEM) photograph of spinel-type Li-Ni-Mn-O multi-pore micron rod.
Fig. 3 is the charging and discharging curve that the second time being the lithium battery of positive pole with spinel-type Li-Ni-Mn-O multi-pore micron rod circulates.
The cyclical stability figure that Fig. 4 is is the lithium battery of positive pole with spinel-type Li-Ni-Mn-O multi-pore micron rod.
Specific embodiment
Embodiment:
Have a preparation method for the spinel-type Li-Ni-Mn-O of one dimension loose structure, step is as follows:
1) preparation of the manganese oxalate micron bar of one-dimentional structure
The 20mL 0.4M manganese chloride aqueous solution is mixed with 20mL 0.4M oxalic acid aqueous solution and stirs 20 minutes, precipitation and separation is also dry, namely obtain the manganese oxalate micron bar of one-dimentional structure, Fig. 1 is the scanning electron microscope (SEM) photograph of manganese oxalate micron bar, and the diameter showing this manganese oxalate micron bar in figure is 1-3 μm.
2) preparation of spinel-type Li-Ni-Mn-O
The manganese oxalate micron bar above-mentioned 500mg with one-dimentional structure in air atmosphere 500 DEG C of roastings 10 hours, then mix with 181mg bis-hydration lithium acetate and 210mg tetra-hydration nickel acetate, by the 700 DEG C of roastings 10 hours under air or oxygen atmosphere of gained mixture, prepare spinel-type Li-Ni-Mn-O, Fig. 2 is the scanning electron microscope (SEM) photograph of spinel-type Li-Ni-Mn-O multi-pore micron rod, the diameter showing this multi-pore micron rod in figure is 1-3 μm, and length is 10-20 μm.
The spinel-type Li-Ni-Mn-O multi-pore micron of above-mentioned preparation rod is used as the application of high-performance button-type lithium cell positive pole, step is as follows:
1) preparation of Li-Ni-Mn-O positive pole
75wt% porous spinelle type Li-Ni-Mn-O, 20wt% acetylene black and 5wt% Kynoar are added the even pulpous state of 1-METHYLPYRROLIDONE furnishing, be coated on thickness is 500 μm, diameter is 12mm aluminium foil disk as pole piece, pole piece was 100 DEG C of vacuumizes 12 hours, then 20MPa pressure 1 minute, obtain spinel-type Li-Ni-Mn-O positive plate, wherein the quality of spinel-type Li-Ni-Mn-O is 1mg;
2) button cell assembling
Be that the lithium sheet of 2mm cuts off the feet into the disk of diameter 14mm as negative plate using thickness, barrier film is the Celgard 2320 of polyethylene/polypropylene/polyethylene trilamellar membrane composition, electrolyte is ethyl carbonate (EC)/dimethyl carbonate (DMC) solution of concentration 1.0mol/L lithium hexafluoro phosphate (LiPF6), and the volume ratio of EC and DMC is 1:1.Above-mentioned positive and negative plate, barrier film and electrolyte are assembled into CR2032 lithium button cell battery in the glove box being full of argon gas.
This lithium button cell battery performance test:
Fig. 3 is the charging and discharging curve that the second time being the lithium battery of positive pole with spinel-type Li-Ni-Mn-O multi-pore micron rod circulates, and its discharge capacity reaches 133mAh g
-1; The cyclical stability figure that Fig. 4 is is the lithium battery of positive pole with spinel-type Li-Ni-Mn-O multi-pore micron rod, shows in figure: after 200 circulations, capacity remains on 105mAhg
-1, capability retention reaches 79%.
Claims (1)
1. there is a preparation method for the spinel-type Li-Ni-Mn-O of one dimension loose structure, it is characterized in that step is as follows:
1) preparation of the manganese oxalate micron bar of one-dimentional structure
Mixed with oxalic acid or ammonium oxalate solution by manganese salt solution and stirring reaction 20 minutes, precipitation and separation is also dry, and namely obtain the manganese oxalate micron bar of one-dimentional structure, its diameter is 0.2-3 μm, fineness ratio is 1:2-100;
2) preparation of spinel-type Li-Ni-Mn-O
By the above-mentioned manganese oxalate micron bar with one-dimentional structure in the presence of air or oxygen at 300-600 DEG C of roasting 2-15 hour, then mix with lithium source and nickel source, finally by gained mixture 300-900 DEG C of roasting 6-34 hour under air or oxygen atmosphere, prepare spinel-type Li-Ni-Mn-O, it has one dimension loose structure, diameter is 0.2-3 μm, fineness ratio is 1:2-20, average pore size is 10-20 nm, and specific area is 4-7m
2/ g;
Described manganese salt is manganese chloride, manganese sulfate, manganese nitrate or manganese acetate, and the concentration of manganese salt solution is 0.05-1.5 mol/L; The concentration of oxalic acid or ammonium oxalate solution is 0.05-1.5 mol/L; Manganese salt solution and oxalic acid or ammonium oxalate solution volume ratio are 1:1-8;
Described lithium source is lithium hydroxide, lithium nitrate or lithium acetate, and nickel source is nickel acetate, nickel nitrate, nickel chloride or nickelous sulfate, and the mol ratio of the lithium in the manganese in manganese oxalate micron bar, lithium source and the nickel in nickel source is 1.5:1-1.05:0.5.
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| CN103367739A (en) * | 2013-07-18 | 2013-10-23 | 桂林电子科技大学 | Ellipsoidal porous-structured lithium manganate or nickel lithium manganate positive electrode material and preparation method thereof |
| CN103943848B (en) * | 2014-04-23 | 2016-05-11 | 合肥工业大学 | The preparation method of the bar-shaped structure cobalt-base anode material for lithium-ion batteries of a kind of porous |
| CN104282889B (en) * | 2014-09-11 | 2017-05-03 | 浙江南都电源动力股份有限公司 | Preparation method of manganese oxalate feed liquor and spinel lithium manganate |
| CN105609753B (en) * | 2015-12-14 | 2019-04-30 | 青岛大学 | The preparation method of one-dimensional multi-layer porous fibrous anode material for lithium-ion batteries |
| CN111924882A (en) * | 2020-07-03 | 2020-11-13 | 山东科源新材料有限公司 | Porous lithium manganate positive electrode material and preparation method thereof |
| CN112811882B (en) * | 2021-01-11 | 2022-04-22 | 湖南省美程陶瓷科技有限公司 | High-stability sensor ceramic material and preparation method thereof |
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| WO2016198033A1 (en) * | 2015-06-10 | 2016-12-15 | Forschungszentrum Jülich GmbH | Method for producing nanostructured layers |
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