CN103904322B - A kind of three-dimensional porous nano carbon compound LiMn2O4 spherical anode material and preparation method thereof - Google Patents
A kind of three-dimensional porous nano carbon compound LiMn2O4 spherical anode material and preparation method thereof Download PDFInfo
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- CN103904322B CN103904322B CN201410131345.0A CN201410131345A CN103904322B CN 103904322 B CN103904322 B CN 103904322B CN 201410131345 A CN201410131345 A CN 201410131345A CN 103904322 B CN103904322 B CN 103904322B
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The present invention discloses a kind of three-dimensional porous nano carbon compound LiMn2O4 spherical anode material and preparation method thereof.With poly-(acrylamide and acrylic acid) microgel ball for template, by Mn
2+the carboxylate radical (-COO of ionic adsorption in the three-dimensional macromolecule network of microgel
-) on group; Raise the pH value in poly-(acrylamide and acrylic acid) microgel ball, make Mn
2+ion in-situ hydrolysis, generates Mn (OH)
2nucleus, is deposited in the space of three-dimensional macromolecule network formation, forms nano composite polymer microballoon; The nano composite polymer microballoon of gained is placed in tube furnace, high-temperature calcination under inert atmosphere, prepares three-dimensional porous nano carbon compound LiMn2O4 spherical anode material.Positive electrode provided by the invention has the advantages such as excellent high temperature cyclic performance and high rate charge-discharge performance, can be widely used in lithium battery and produce.
Description
Technical field
The present invention relates to the preparation of a kind of porous spherical anode material for lithium-ion batteries and method thereof, belong to technical field of chemical power.
Background technology
Lithium ion battery, as a kind of secondary cell reused, has the long-life, use safety, can big current fast charging and discharging, high temperature resistant, Large Copacity, and self-discharge rate is low, memory-less effect, and energy density is large, environmental protection.After nineteen ninety, Sony Corporation was by lithium ion battery commercialization, lithium ion battery is as successful secondary power supply.
The research of anode material for lithium-ion batteries remains the key factor of restriction lithium ion battery motorization, business-like positive electrode has cobalt acid lithium, LiMn2O4, LiFePO 4 etc., cobalt acid lithium to be taken the lead in commercialization by Sony Corporation, but because cobalt resource is deficient, expensive, the factors such as environmental pollution is larger, a kind of novel anode material of active demand.
Since Goodenough in 1997 etc. have proposed LiFePO 4 first as since anode material for lithium-ion batteries, lithium iron phosphate cathode material becomes new study hotspot gradually both at home and abroad.LiFePO 4 electrode material is mainly used in power lithium-ion battery, and domestic-developed goes out Large Copacity ferrous phosphate lithium battery, and its security performance and cycle life are that other materials is incomparable.The advantages such as especially it is nontoxic, pollution-free, security performance is good, raw material sources is extensive, low price, life-span length, become important anode material for lithium-ion batteries.But LiFePO 4 tap density is low, reduce the energy density of battery.The conductive capability of ferrousphosphate lithium material is poor, and cryogenic property is also undesirable.
Another kind of that anode material for lithium-ion batteries-LiMn2O4 has voltage platform is high, and low price, environmental friendliness, security performance advantages of higher, is applicable to the electrokinetic cell of electric tool of new generation, electric motor car and hybrid vehicle.But the high temperature cyclic performance of LiMn2O4 is poor, limit its extensive use.The principal element affecting lithium manganate material high temperature cyclic performance has: the dissolving of (1) manganese; (2) Jahn-Teller effect.Research finds, by Surface coating and bulk phase-doped dissimilar metal ion, can improve high temperature cyclic performance and the high rate capability of LiMn2O4.The former reduces LiMn2O4 nano-material surface and directly contacts with electrolytical by reducing the specific area of material, thus alleviate the dissolving of manganese, and cushions the crystal volume change in LiMn2O4 charge and discharge process; The latter strengthens the stability of LiMn2O4 crystal structure.
Anode material for lithium-ion batteries has received to be paid close attention to and a large amount of reports widely, such as, application number is that the Chinese patent literature of CN201110253754.4 reports modified lithium manganate cathode material and preparation method thereof, the method passes through Na, Mg, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, Zr, Nb, Ce, one or more doped with metal elements in Nd and Dy, first the oxide particle on its surface reacts with the HF of trace in electrolyte, reduce the dissolving of manganese element in material of main part, modified lithium manganate cathode material is made to have good high temperature cyclic performance and high rate performance.Being distributed in bulk material surface because oxide particle is discontinuous, is not coated bulk material surface, therefore, avoids the increase causing impedance because of the existence of coating layer.Application number is the preparation method that the Chinese patent literature of CN201210440232.X reports a kind of coated modified carbon manganate cathode material for lithium; the method passes through dissolved organic carbon source under the effect of carbided catalyst; material surface is made to avoid it directly to contact electrolyte by carbon modification raising electrode conductivuty, the surface chemistry improving active material, guard electrode, thus improve cycle life and the high rate performance of electrode material.Synthesis step comprises: (1) synthetic lithium manganate nano particle; (2) in its Surface coating nano-sized carbon.This technique is consuming time, complex process not only, and needs to solve simultaneously and prevent nanoparticle aggregate and even coated each nano grain surface two key technical problems, is difficult to large-scale industrial production nano-carbon coated LiMn2O4 composite material.
Summary of the invention
The invention reside in and a kind of three-dimensional porous nano carbon compound LiMn2O4 spherical anode material and preparation method thereof is provided.
Three-dimensional porous nano carbon compound LiMn2O4 spherical anode material provided by the invention has loose structure and spherical morphology, and the LiMn2O4 nano particle being 20 ~ 35nm by particle diameter is formed with the amorphous carbon being coated on its surface, and microspherulite diameter is 5 ~ 50 μm.
The preparation method of three-dimensional porous nano carbon compound LiMn2O4 spherical anode material provided by the invention is, adopts poly-(acrylamide and acrylic acid) microgel ball to be template, Mn
2+the space that ion is formed at three-dimensional macromolecule network, i.e. microreactor situ hydrolysis, generate precipitate nucleation, these nucleus generate LiMn2O4 with lithium salts high-temperature calcination in microreactor, simultaneously, carbonized polymers strand is coated on LiMn2O4 nano grain surface, and prepare three-dimensional porous nano carbon compound LiMn2O4 spherical anode material, preparation process is as follows:
Step one, with poly-(acrylamide and acrylic acid) microgel ball of emulsion polymerization preparation;
Step 2, polymer microgel ball step one obtained is immersed in containing Mn
2+and Li
+in the aqueous solution of ion and urea, utilize carboxylate radical (-COO in poly-(acrylamide and acrylic acid) microgel ball
-) and Mn
2+and Li
+electrostatic attraction effect between ion, by Mn
2+and Li
+ionic adsorption wherein;
Step 3, raised temperature to 70 ± 2 DEG C, make urea decomposition and discharge NH
3, improve the pH value of the aqueous solution in poly-(acrylamide and acrylic acid) microgel ball, cause Mn
2+the space that ion is formed at three-dimensional macromolecule network, i.e. microreactor situ hydrolysis, generates Mn (OH)
2nucleus, rapid draing obtains nano composite polymer microballoon;
Step 4, is placed in tube furnace by nano composite polymer microballoon, first logical oxygen 200 DEG C process 2 hours, more logical nitrogen temperature to 450 ± 5 DEG C process 120 ± 3 minutes, are finally warming up to 700 ± 2 DEG C of process 240 ± 6 minutes.
Further, described Mn
2+ion is from one or more in manganese sulfate, manganese nitrate, manganese chloride and manganese acetate; Described Li
+ion is from one or more in lithium sulfate, lithium nitrate, lithium chloride and lithium acetate.
Further, in step 4, being 0.2 DEG C/min from the programming rates of 200 DEG C to 450 DEG C, is 0.5 DEG C/min from the programming rates of 450 DEG C to 700 DEG C.
Based on Li
+ion embeds-deviates from the lithium ion battery electrode material of electrochemical reaction mechanism, and electrode material nanometer can shorten Li
+the migration distance of ion, improves the electrochemical kinetics performance of electrode material.Meanwhile, the migration velocity of electronics is also sufficiently fast, and electrode material just can be made to meet the requirement of fast charging and discharging.Therefore, at nano-electrode material Surface coating electron conducting layer, form three-dimensional ion/electronics hybrid conductive network, the micro-nano combination electrode material prepared thus has excellent fast charging and discharging ability and cycle performance.
Three-dimensional porous nano carbon compound LiMn2O4 spherical anode material provided by the invention has excellent high temperature cyclic performance and high rate charge-discharge performance; Because of the feature that it has three-dimensional porous structure and the even coating LiMn 2 O nano particle of nano-sized carbon, not only can reduce the meltage of LiMn2O4 in electrolyte solution, the change in volume of LiMn2O4 nano particle in charge and discharge process can also be cushioned.Compared with existing lithium manganate material, three-dimensional porous nano carbon compound LiMn2O4 spherical anode material of the present invention becomes micron level spherical powder by the LiMn2O4 nanoparticle aggregate that the nanometer carbochain of polymer molecular chain pyrolysis is coated, have loose structure and three-dimensional ion/electronics hybrid conductive network, high rate performance is excellent.Because it is micron-size spherical particles, specific area is low, not only effectively reduces the dissolving of manganese and improves cycle performance, and is conducive to the electrode fabrication of existing coating method.In addition, nanometer carbochain, to the constraint effect of LiMn2O4 nano particle, can be alleviated the change in volume in LiMn2O4 nano particle charge and discharge process, improve cycle performance further.
Preparation method provided by the invention is simple, material morphology and pore structure controlled, there is very large industrial production value.Can, by the size of the three-dimensional mesh structure Effective Regulation LiMn2O4 nano particle of polymer microgel template and pattern, poly-(acrylamide and acrylic acid) microgel ball be adopted to be template, Mn
2+the space that ion is formed at three-dimensional macromolecule network, i.e. microreactor situ hydrolysis, generate precipitate nucleation, these nucleus generate LiMn2O4 with lithium salts high-temperature calcination in microreactor.Meanwhile, polymer molecular chain carbonization is coated on LiMn2O4 nano grain surface, prepares three-dimensional porous nano carbon compound LiMn2O4 spherical anode material.Due to the space confinement effect of the three-dimensional macromolecule network in poly-(acrylamide and acrylic acid) microgel ball, in high-temperature burning process, the growth of LiMn2O4 nano particle is suppressed, therefore, the LiMn2O4 nano particle that the three-dimensional porous nano carbon compound LiMn2O4 spherical anode material of preparation is 20 ~ 35nm by particle diameter is formed with the amorphous carbon being coated on its surface, and microspherulite diameter scope is 5 ~ 50 μm.At normal temperatures, in the voltage range of 4.3-3V, three-dimensional porous nano carbon compound LiMn2O4 spherical anode material is respectively 123,122,114 and 106mAh/g with the specific capacity discharged first in 12,120,600 and 1200mA/g current density.Due to the coating function of nano-sized carbon, it is respectively 91% and 82% at normal temperature (25 DEG C) and high temperature (65 DEG C) the 1C capability retention after 200 times that circulates.
Accompanying drawing explanation
Fig. 1 is the SEM photo of three-dimensional porous nano carbon compound LiMn2O4 spherical anode material prepared by embodiment.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
The preparation method of the three-dimensional porous nano carbon compound LiMn2O4 spherical anode material provided is provided, specific as follows:
Step one, first adds 700 milliliters of normal heptanes in 2000 milliliters of there-necked flasks, then adds 7.50g surfactant Span-80 and 0.75g surfactant Tween-80, stirs under nitrogen protection, controls bath temperature 40 DEG C, obtains oil phase;
In 100 ml beakers, add 50 ml deionized water, then add 9.60g acrylamide monomer dissolve obtain solution A.Taking NaOH solid 0.85g is dissolved in 10 ml deionized water, in ice-water bath after cooling, then drips 3.5 milliliters of acrylic monomerss and obtains solution B in NaOH solution; Solution A and B are mixed, then in this mixed solution, adds crosslinking agent methylene-bisacrylamide 0.7g, finally add the ammonium persulfate solution that 5 ml concns are 1 mol/L, be made into aqueous phase;
Joined by aqueous phase in oil-based system, logical nitrogen, after 30 minutes, adds the tetramethylethylenediamine that 10 ml concns are 0.5 mol/L, increases the temperature to 60 DEG C, polymerization reaction 5 hours; Product, after water and acetone replace washing 3 times, dries naturally, obtains poly-(acrylamide and acrylic acid) powder of white;
Step 2, polymer powder 1g step one obtained is soaked in 100 milliliters and contains in the mixed solution of 0.1 mol/L manganese nitrate and 0.05 mol/L urea, and room temperature low rate mixing 12 hours, then raised temperature to 90 DEG C, react 2 hours, filters, obtain filter residue;
Step 3, filter residue adds in the 10 ml water solution containing 0.51 molar nitric acid lithium, and 70 DEG C of freeze-day with constant temperature 10 hours, obtain presoma;
Step 4, presoma step 3 obtained is placed in tube-type atmosphere furnace, first logical oxygen 200 DEG C process 2 hours, then after logical nitrogen half an hour, is warmed up to 450 DEG C, is incubated 2 hours with the speed of 0.2 DEG C/min; 700 DEG C are warming up to again, insulation 4h with the speed of 0.5 DEG C/min;
Finally, cool to room temperature with the furnace, pulverize and sieve and obtain the coated three-dimensional porous ball-type manganate cathode material for lithium of carbon; Roasting, cooling, pulverizing, obtain three-dimensional porous nano carbon compound LiMn2O4 spherical anode material.The LiMn2O4 nano particle that the three-dimensional porous nano carbon compound LiMn2O4 spherical anode material of preparation is 20 ~ 35nm by particle diameter is formed with the amorphous carbon being coated on its surface, and microspherulite diameter scope is 5 ~ 50 μm.
Three-dimensional porous nano carbon compound LiMn2O4 spherical anode material, acetylene black, Kynoar mass ratio 8: 1: 1 are scattered in 1-METHYLPYRROLIDONE, stir form slurry at normal temperatures and pressures, evenly be coated in aluminium foil surface, 120 DEG C of vacuumizes, are cut into the thin rounded flakes that diameter is 1cm after roll-in.With it for positive pole, assemble button cell with cathode of lithium and Celgard2300 perforated membrane, electrolyte is the LiPF of 1mol/L
6ethylene carbonate (EC) and dimethyl carbonate (DMC) solution (both mass ratioes are 1: 1).
Constant current charge-discharge technology is used to test button cell, probe temperature is 25 DEG C, charging and discharging currents density is respectively 12,120,600 and 1200mA/g, filling a final voltage is 4.3V, final discharging voltage is 3.0V, and first discharge specific capacity is respectively 123,122,114 and 106mAh/g.Three-dimensional porous nano carbon compound LiMn2O4 spherical anode material is respectively 91% and 82% at normal temperature (25 DEG C) and high temperature (65 DEG C) the 120mA/g capability retention after 200 times that circulates.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.Be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will not be restricted to embodiment illustrated herein, but the scope consistent with principle disclosed herein and novelty.
Claims (3)
1. a preparation method for three-dimensional porous nano carbon compound LiMn2O4 spherical anode material, is characterized in that, adopts poly-(acrylamide and acrylic acid) microgel ball to be template, Mn
2+the space that ion is formed at three-dimensional macromolecule network, i.e. microreactor situ hydrolysis, generate precipitate nucleation, these nucleus generate LiMn2O4 with lithium salts high-temperature calcination in microreactor, simultaneously, carbonized polymers strand is coated on LiMn2O4 nano grain surface, and prepare three-dimensional porous nano carbon compound LiMn2O4 spherical anode material, preparation process is as follows:
Step one, with poly-(acrylamide and acrylic acid) microgel ball of emulsion polymerization preparation;
Step 2, polymer microgel ball step one obtained is immersed in containing Mn
2+with in the aqueous solution of urea, raised temperature to 90 DEG C, reacts 2 hours, utilizes carboxylate radical (-COO in poly-(acrylamide and acrylic acid) microgel ball
-) and Mn
2+electrostatic attraction effect between ion, by Mn
2+ionic adsorption wherein, obtains filter residue;
Step 3, filter residue adds Li
+the aqueous solution, raised temperature to 70 ± 2 DEG C, make urea decomposition and discharge NH
3, improve the pH value of the aqueous solution in poly-(acrylamide and acrylic acid) microgel ball, cause Mn
2+the space that ion is formed at three-dimensional macromolecule network, i.e. microreactor situ hydrolysis, generates Mn (OH)
2nucleus, rapid draing obtains nano composite polymer microballoon;
Step 4, is placed in tube furnace by nano composite polymer microballoon, first logical oxygen 200 ± 3 DEG C process 120 ± 3 minutes, more logical nitrogen temperature to 450 ± 5 DEG C process 120 ± 3 minutes, are finally warming up to 700 ± 2 DEG C of process 240 ± 6 minutes.
2. the preparation method of a kind of three-dimensional porous nano carbon compound LiMn2O4 spherical anode material according to claim 1, is characterized in that, described Mn
2+ion is from one or more in manganese sulfate, manganese nitrate, manganese chloride and manganese acetate; Described Li
+ion is from one or more in lithium sulfate, lithium nitrate, lithium chloride and lithium acetate.
3. the preparation method of a kind of three-dimensional porous nano carbon compound LiMn2O4 spherical anode material according to claim 1, it is characterized in that, in described step 4, being 0.2 DEG C/min from the programming rates of 200 DEG C to 450 DEG C, is 0.5 DEG C/min from the programming rates of 450 DEG C to 700 DEG C.
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| CN107364893B (en) * | 2017-06-29 | 2019-04-05 | 宁波吉电鑫新材料科技有限公司 | A kind of templated synthesis perovskite lithium ion battery negative material and preparation method thereof |
| CN109244444B (en) * | 2018-08-29 | 2021-06-18 | 湘潭大学 | Niobium-doped lithium-rich manganese-based layered oxide positive electrode material and preparation method thereof |
| CN111233042B (en) * | 2020-01-16 | 2022-03-11 | 阜阳师范大学 | Lithium manganate positive electrode material precursor, lithium manganate positive electrode material and preparation method thereof |
| CN113782743B (en) * | 2021-08-27 | 2022-07-12 | 合肥国轩高科动力能源有限公司 | Lithium ion battery positive electrode material and preparation method and application thereof |
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| CN102916178A (en) * | 2012-11-07 | 2013-02-06 | 彩虹集团公司 | Preparation method of carbon cladding modified lithium manganate anode material |
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