CN104178929A - Method for preparing LiNi1/3Co1/3Mn1/3O2 fibrous material by electrostatic spinning - Google Patents
Method for preparing LiNi1/3Co1/3Mn1/3O2 fibrous material by electrostatic spinning Download PDFInfo
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- CN104178929A CN104178929A CN201410407612.2A CN201410407612A CN104178929A CN 104178929 A CN104178929 A CN 104178929A CN 201410407612 A CN201410407612 A CN 201410407612A CN 104178929 A CN104178929 A CN 104178929A
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- fibrous material
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 33
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 title claims abstract description 21
- 239000002657 fibrous material Substances 0.000 title claims abstract description 17
- 238000009987 spinning Methods 0.000 claims abstract description 55
- 239000000835 fiber Substances 0.000 claims abstract description 31
- 239000002121 nanofiber Substances 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000002459 sustained effect Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000008367 deionised water Substances 0.000 abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Fibers (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention discloses a method for preparing a LiNi1/3Co1/3Mn1/3O2 fibrous material by electrostatic spinning and belongs to the technical field of lithium ion battery electrode materials and preparation thereof. The method includes: taking deionized water as a dissolvent, regulating solution viscosity through polyvinylpyrrolidone, then adding a lithium source, a nickel source, a cobalt source and a manganese source to prepare a spinning solution, preparing a nanofiber film by a electrostatic spinning technique, and then sintering the nanofiber film to obtain the LiNi1/3Co1/3Mn1/3O2 fibrous material. The fibrous material prepared by the method is smooth in surface, small in fibre diameter and large in specific surface area and has good charge and discharge performance and large storage capacity, the preparation method is simple in technology, reaction condition parameters are easy to control, sintering temperature is low, and large-scale industrialization of cathode materials of lithium nickelate, lithium cobaltate and lithium manganate are benefited.
Description
Technical field
The invention belongs to lithium ion battery electrode material and preparing technical field thereof, be specifically related to a kind of electrostatic spinning technique and prepare LiNi
1/3co
1/3mn
1/3o
2the method of fibrous material.
Background technology
LiNi
1/3co
1/3mn
1/3o
2it is a kind of Olivine-type Cathode Material in Li-ion Batteries.It is high that it has theoretical capacity, Stability Analysis of Structures, and the advantage such as cycle performance is good, and discharge voltage range is wide, cheap, environmentally friendly, is considered to the most promising anode material for lithium-ion batteries, and is expected to be used on the electric automobile taking lithium ion battery as power.
Traditional preparation method mainly contains following several: high temperature solid phase synthesis, sol-gel process, coprecipitation, hydro-thermal method etc.But all there are some intrinsic shortcomings in these methods, as: the shortcoming such as synthesis temperature is high, synthesis cycle is long, controlled condition is harsh, cost is high and the large current discharging capability of synthetic material is poor, these are all limiting Li
1/3ni
1/3co
1/3mnO
2extensive industrialization.
Electrostatic spinning is a kind of New Processing of the simple and effective nanofiber produced, its principle is that spinning liquid is flowed out from spinning appts, under voltage effect, overcome the surface tension of spray silk liquid self and viscoelastic power and form jet, along with the volatilization of solvent and solidifying of melt, jet finally forms fiber on receiving system.Adopt method of electrostatic spinning to prepare nanofiber positive electrode, this nanometer fibrous positive electrode can not only increase the specific area of active material, increase operation rate, increase battery specific capacity, also because its porous and fiber are interconnected to form the design features such as interpenetrating networks, can accelerate ion, electrical conductivity, make battery there is excellent cycle performance and high rate performance.Compared with other preparation methods, electrostatic spinning technique can be prepared the positive electrode that more meets the requirement of lithium-ion-power cell chemical property, but at present electrostatic spinning is also rarely had to report for the preparation of the technology of nickle cobalt lithium manganate nanofiber.
Summary of the invention
Goal of the invention of the present invention is: for the problem of above-mentioned existence, provide a kind of and novel prepare anode material for lithium-ion batteries LiNi with method of electrostatic spinning
1/3co
1/3mn
1/3o
2technical method, it is high that products obtained therefrom of the present invention has specific capacity, the advantages such as good cycle.
It is as follows that the present invention realizes the technical scheme that above-mentioned purpose adopts:
Electrostatic spinning is prepared LiNi
1/3co
1/3mn
1/3o
2the method of fibrous material, comprises the following steps:
(1) configuration of spinning solution: measure 25 parts of deionized waters in beaker, adding quality is 10% polyvinylpyrrolidone (PVP) of water, then add respectively a certain amount of lithium source, nickel source, He Meng source, cobalt source, the concentration that makes the CATION Li element in solution is 1.6mol/L, and the concentration of Ni, Co, Mn element is 0.8mol/L; Add at every turn and fashionablely guarantee that above institute adds material and dissolve completely; After continuing to stir 8h, standing 4h obtains spinning solution;
(2) electrostatic spinning: be 20-25 DEG C in temperature, under the environment of humidity≤30%, carry out electrostatic spinning, the above-mentioned spinning solution preparing is joined in syringe, syringe needle connects positive source, cylinder receiving system connects power cathode, the top of the spinning head of syringe and cylinder receiving system is at sustained height, be 25-50cm accepting distance, voltage is 8-17kV, the spinning solution speed of injecting is 0.01-0.1ml/min, the rotating speed of cylinder receiving device is to carry out spinning under the condition of 30-50r/min, nano-fiber material is wrapped on cylinder uniformly, spinning 18h has obtained nano-fiber film,
(3) sintering: fiber membrane is placed in to vacuum drying chamber vacuumize 4-8h under 90-120 DEG C of condition; Dried fiber membrane is placed in to Muffle furnace and is heated to 450 DEG C of insulation 8h, finally within the scope of 600-750 DEG C, sintering 6-18h obtains LiNi
1/3co
1/3mn
1/3o
2nano-fiber material.
Wherein, described nickel source compound is the one in nickelous carbonate, nickel acetate and nickel nitrate.
Described cobalt source compound is the one in cobalt acid nickel, cobalt acetate and cobalt nitrate.
Described manganese source compound is the one in manganese carbonate, manganese acetate and manganese nitrate.
Described Li source compound is the one in lithium carbonate, lithium formate, lithium hydroxide, lithium acetate and lithia.
In electrospinning process, the factor that affects fibre forming comprises SOLUTION PROPERTIES, process conditions, ambient parameter, and wherein, SOLUTION PROPERTIES is the principal element that affects fibre morphology and diameter distribution, and the chemical property of material is had a direct impact.The applicant, after continuous experiment is groped, has determined the experiment parameter in technique scheme, has determined the consumption of polyvinylpyrrolidone, solution viscosity can be adjusted to suitable viscosity, increases the spinnability of spinning solution, is conducive to form smooth continuous fibers.The present invention is by the mode spinning of solution, and each component is evenly distributed in solution, can make the chemical property of electrode material more stable.
Aspect process conditions, applying voltage is the precondition that generates fiber, along with voltage increases, be conducive to generate thinner fiber, mutually restrict with voltage and accept distance, accept distance larger, need to add a larger voltage and just can obtain fiber, accept distance and also have influence on being dried and refinement of fibre bundle, distance is too short, solvent can not get abundant volatilization and just bonds together, and volatilization not exclusively also can cause that the change of fibre diameter is large.The present invention verifies by experiment, has determined that preferred acceptance distance is 25-50cm, and voltage is 8-17kV, ensures that fibre diameter is even and very thin.
The speed of flow rate of liquid also has impact to fibre diameter, and too spinning speed is low slowly, and fiber can not get timely stretching too soon.The present invention is according to spinning solution character, and preferably the speed of injecting is 0.01-0.1ml/min, and the rotating speed of cylinder receiving device is 30-50r/min.
In electrostatic spinning process, the present invention is more preferably 25cm accepting distance, and voltage is 14kV, and the spinning solution speed of injecting is 0.06ml/min, carries out spinning under the condition that the rotating speed of cylinder receiving device is 30r/min.
In addition, the temperature of environment, humidity directly affect the volatile dry degree of solvent, dry too fast, can make liquid be bonded at spinning nozzle, hinder spinning and carry out, and it is large that the diameter of fiber also can become.The preferred temperature of the present invention is 20-25 DEG C, humidity≤30%.
After electrostatic spinning process completes, also need, to the fiber membrane sintering that heats up stage by stage, to improve LiNi
1/3co
1/3mn
1/3o
2the degree of crystallinity of nano-fiber material, makes physical dimension homogeneous, effectively reduces surface energy, thereby the coulomb repulsion between lithium ion is reduced, and strengthens the capacity of lithium ion.Fiber membrane being carried out to vacuumize before sintering of the present invention, is in order not make film yielding and affect chemical property.
In sum, than the preparation method of prior art, the beneficial effect that the present invention has is:
(1) in spinning process, because spinning solution flows very slowly, spinning solution can utilize fully, and the utilization rate of raw material is very high, and spinning process is continuous, prepares the speed of nano silk.
(2) the present invention is by controlling the various parameters in preparation process, and the fibre diameter that obtains is little, even thickness and continuously, its specific area is larger than also.Fibrous material diameter is smaller, and the evolving path of lithium ion in nanofiber is short, insert depth is shallow, is conducive to lithium ion deintercalation fast in nano-fiber material.Fibrous material specific area is large, can increase the contact area of electrode and electrolyte, reduces polarization of electrode phenomenon in electrochemical reaction process, is conducive to the transmission of lithium ion; Therefore the ionic conductivity of material and electron conduction are all significantly improved, and have good discharge performance.
(3) on fiber axial direction, have a lot of lattice defects or blemish through electro-spinning standby nano-fiber material, this can be for lithium ion provides more reaction site, and improve the storage lithium performance of material.
(4) technique of the present invention is simple, and reaction condition parameter is easy to control, and it is low that sintering temperature is compared high temperature solid phase synthesis (being generally 1000 DEG C), can reduce the energy consumption of synthetic material, reduced cost.
Brief description of the drawings
Fig. 1 is the XRD collection of illustrative plates of sample in the embodiment of the present invention 3.
Fig. 2 is the SEM figure of sample in the embodiment of the present invention 3.
Fig. 3 is the charging and discharging curve figure of sample in the embodiment of the present invention 3.
Detailed description of the invention
The present invention adopts method of electrostatic spinning to prepare anode material for lithium-ion batteries LiNi
1/3co
1/3mn
1/3o
2, mainly comprise the process of preparation, electrostatic spinning process and the sintering of spinning solution.Key point of the present invention is the selection of polymer, the control of spinning fluid viscosity, cation concn, the control of spinning process technological parameter ambient parameter, the technique of sintering.The invention provides a kind of novel positive electrode LiNi for preparing
1/3co
1/3mn
1/3o
2method, it is high that gained positive electrode has specific capacity, the advantages such as good cycle, it is simple that institute's employing method has technique, reaction condition parameter is easy to control, the advantage such as sintering temperature is low.Below by specific embodiments and the drawings, the invention will be further described.
Embodiment 1
Electrostatic spinning is prepared LiNi
1/3co
1/3mn
1/3o
2the method of fibrous material, comprises the following steps:
(1) configuration of spinning solution: measure 25ml deionized water in beaker, adding quality is 10% polyvinylpyrrolidone (PVP) of water, then add respectively lithium carbonate, nickel nitrate, cobalt acetate and the manganese nitrate of 0.2mol, the concentration that makes the Li element in solution is 1.6mol/L, and the concentration of Ni, Co, Mn element is 0.8mol/L; Add at every turn and fashionablely guarantee that above institute adds material and dissolve completely; After continuing to stir 8h, standing 4h obtains spinning solution;
(2) electrostatic spinning: be 20-25 DEG C in temperature, under the environment of humidity≤30%, carry out electrostatic spinning, the spinning solution that step (1) is prepared joins in syringe, syringe needle connects positive source, cylinder receiving system connects power cathode, the top of the spinning head of syringe and cylinder receiving system is at sustained height, be 25cm accepting distance, voltage is 8kV, the spinning solution speed of injecting is 0.01ml/min, the rotating speed of cylinder receiving device is to carry out spinning under the condition of 30r/min, nano-fiber material is wrapped on cylinder uniformly, spinning 18h has obtained nano-fiber film,
(3) sintering: fiber membrane is placed in to vacuum drying chamber vacuumize 8h under 90 DEG C of conditions; Dried fiber membrane is placed in to Muffle furnace and is heated to 450 DEG C of insulation 8h, finally within the scope of 600 DEG C, sintering 18h obtains LiNi
1/3co
1/3mn
1/3o
2nano-fiber material.
Embodiment 2
Electrostatic spinning is prepared LiNi
1/3co
1/3mn
1/3o
2the method of fibrous material, comprises the following steps:
(1) configuration of spinning solution: measure 25ml deionized water in beaker, adding quality is 10% polyvinylpyrrolidone (PVP) of water, then add respectively lithium acetate, nickel acetate, cobalt nitrate and the manganese acetate of 0.2mol, the concentration that makes the Li element in solution is 1.6mol/L, and the concentration of Ni, Co, Mn element is 0.8mol/L; Add at every turn and fashionablely guarantee that above institute adds material and dissolve completely; After continuing to stir 8h, standing 4h obtains spinning solution;
(2) electrostatic spinning: be 20-25 DEG C in temperature, under the environment of humidity≤30%, carry out electrostatic spinning, the spinning solution that step (1) is prepared joins in syringe, syringe needle connects positive source, cylinder receiving system connects power cathode, the top of the spinning head of syringe and cylinder receiving system is at sustained height, be 50cm accepting distance, voltage is 17kV, the spinning solution speed of injecting is 0.1ml/min, the rotating speed of cylinder receiving device is to carry out spinning under the condition of 50r/min, nano-fiber material is wrapped on cylinder uniformly, spinning 18h has obtained nano-fiber film,
(3) sintering: fiber membrane is placed in to vacuum drying chamber vacuumize 4h under 120 DEG C of conditions; Dried fiber membrane is placed in to Muffle furnace and is heated to 450 DEG C of insulation 8h, finally at 750 DEG C of temperature, sintering 6h obtains LiNi
1/3co
1/3mn
1/3o
2nano-fiber material.
Embodiment 3
Electrostatic spinning is prepared LiNi
1/3co
1/3mn
1/3o
2the method of fibrous material, comprises the following steps:
(1) configuration of spinning solution: measure 25ml deionized water in beaker, adding quality is 10% polyvinylpyrrolidone (PVP) of water, then add respectively lithium hydroxide, nickelous carbonate, cobalt carbonate and the manganese carbonate of 0.2mol, the concentration that makes the Li element in solution is 1.6mol/L, and the concentration of Ni, Co, Mn element is 0.8mol/L; Add at every turn and fashionablely guarantee that above institute adds material and dissolve completely; After continuing to stir 8h, standing 4h obtains spinning solution;
(2) electrostatic spinning: be 20-25 DEG C in temperature, under the environment of humidity≤30%, carry out electrostatic spinning, the spinning solution that step (1) is prepared joins in syringe, syringe needle connects positive source, cylinder receiving system connects power cathode, the top of the spinning head of syringe and cylinder receiving system is at sustained height, be 25cm accepting distance, voltage is 14kV, the spinning solution speed of injecting is 0.06ml/min, the rotating speed of cylinder receiving device is to carry out spinning under the condition of 30r/min, nano-fiber material is wrapped on cylinder uniformly, spinning 18h has obtained nano-fiber film,
(3) sintering: fiber membrane is placed in to vacuum drying chamber vacuumize 4h under 90 DEG C of conditions; Dried fiber membrane is placed in to Muffle furnace and is heated to 450 DEG C of insulation 8h, finally at 700 DEG C of temperature, sintering 12h obtains LiNi
1/3co
1/3mn
1/3o
2nano-fiber material.
Embodiment 3 gained samples are carried out to XRD analysis, result as shown in Figure 1, as can be seen from the figure, gained LiNi
1/3co
1/3mn
1/3o
2nano-fiber material is α-NaFeO
2type structure, belongs to
space group.It is carried out to SEM scanning, and result as shown in Figure 2, shows that the sample sintering of gained is front for evenly thread, and fibrous material continuous uniform, smooth surface, and fibre diameter is approximately 250～300nm, does not have particle to adhere to its surface; The basic Rod-like shape that keeps after sintering, the diameter of club shaped structure is probably 140～200nm, and length is probably several to tens microns, and this club shaped structure of material is mainly supported by carbon.
The sample sets that embodiment 1-3 is obtained is dressed up button cell and under 0.1C multiplying power, is carried out cycle charge discharge electric performance test, its first discharge capacity and circulation 25 times after discharge capacity in table 1, wherein the charging and discharging curve of the sample of embodiment 3 is as shown in Figure 3.
Table 1 discharge capacity test result
In sum, the present invention, by the method for electrostatic spinning, has successfully made LiNi
1/3co
1/3mn
1/3o
2nano-fiber material, gained fibrous material continuous uniform, smooth surface, fibre diameter is little, and specific area is large, has good charge-discharge performance and larger memory capacity.
Claims (3)
1. electrostatic spinning is prepared LiNi
1/3co
1/3mn
1/3o
2the method of fibrous material, is characterized in that comprising the following steps:
(1) configuration of spinning solution: measure 25 parts of deionized waters in beaker, adding quality is 10% polyvinylpyrrolidone (PVP) of water, then add respectively a certain amount of lithium source, nickel source, He Meng source, cobalt source, make the concentration of the CATION Li element in solution be 1.6mol/L, the concentration of Ni, Co, Mn element is 0.8mol/L; Add at every turn and fashionablely guarantee that above institute adds material and dissolve completely; After continuing to stir 8h, standing 4h obtains spinning solution;
(2) electrostatic spinning: be 20-25 DEG C in temperature, under the environment of humidity≤30%, carry out electrostatic spinning, the above-mentioned spinning solution preparing is joined in syringe, syringe needle connects positive source, cylinder receiving system connects power cathode, the top of the spinning head of syringe and cylinder receiving system is at sustained height, be 25-50cm accepting distance, voltage is 8-17kV, the spinning solution speed of injecting is 0.01-0.1ml/min, the rotating speed of cylinder receiving device is to carry out spinning under the condition of 30-50r/min, nano-fiber material is wrapped on cylinder uniformly, spinning 18h has obtained nano-fiber film,
(3) sintering: fiber membrane is placed in to vacuum drying chamber vacuumize 4-8h under 90-120 DEG C of condition; Dried fiber membrane is placed in to Muffle furnace and is heated to 450 DEG C of insulation 8h, finally within the scope of 600-750 DEG C, sintering 6-18h obtains LiNi
1/3co
1/3mn
1/3o
2nano-fiber material.
2. electrostatic spinning according to claim 1 is prepared LiNi
1/3co
1/3mn
1/3o
2the method of fibrous material, is characterized in that: described nickel source compound is the one in nickelous carbonate, nickel acetate and nickel nitrate; Described cobalt source compound is the one in cobalt acid nickel, cobalt acetate and cobalt nitrate; Described manganese source compound is the one in manganese carbonate, manganese acetate and manganese nitrate; Described Li source compound is the one in lithium carbonate, lithium formate, lithium hydroxide, lithium acetate and lithia.
3. electrostatic spinning according to claim 2 is prepared LiNi
1/3co
1/3mn
1/3o
2the method of fibrous material, is characterized in that: in described electrostatic spinning process, be to accept distance for 25cm, voltage is 14kV, and the spinning solution speed of injecting is 0.06ml/min, carries out spinning under the condition that the rotating speed of cylinder receiving device is 30r/min.
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