CN102255083A - Layered manganese-based composite material for power-type lithium ion battery and preparation method thereof - Google Patents
Layered manganese-based composite material for power-type lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a layered manganese-based composite material Li(MnxNiyCo1-x-y)O2 for power-type lithium ion batteries and a preparation method thereof; the cathode material adopts a lithium source, a manganese source, a nickel source, a cobalt source as raw materials, adopts a sodium salt as a medium; the molar ratio of Na:Mn:Ni:Co is 1:(0.5<=x<1.0):(0<=y<=0.5):(1-x-y), and the amount of substance of the mixed lithium source is 4-10 times the mole number of the sodium salt. The preparation method comprises the following steps: 1) weighing the lithium source, the manganese source, the nickel source, the cobalt source, and the sodium salt according to the above molar ratio respectively; 2) pulverizing the manganese source, the nickel source, and the cobalt source, dissolving in water, dropwisely adding excessive NH4OH into the solution to form a M(OH)2 coprecipitate, wherein M=(Mn, Ni and Co), performing suction filtration, washing to be neutral, and drying in an oven; 3) adding the sodium salt, fully and well mixing in a planetary ball mill, pulverizing the mixture, pressing to form a module; 4) putting the module into a high-frequency reaction vessel, calcining at a constant temperature to obtain a layered precursor Na(MnxNiyCo1-x-y)O2; 5) crushing and pulverizing the precursor Na(MnxNiyCo1-x-y)O2, adding into a prepared lithium source solution for ion exchange; 6) filtering, washing, drying to obtain the cathode material of layered Li(MnxNiyCo1-x-y)O2 for lithium ion batteries.
Description
Technical field
The present invention relates to stratiform manganese based composites of a kind of lithium ion battery material and preparation method, particularly a kind of power-type lithium ion battery and preparation method thereof, belong to the lithium ion battery material technical field.
Background technology
World today's energy day is becoming tight; energy crisis consciousness is accepted by everybody gradually; this also forces various countries competitively to develop the new energy; as solar energy, wind energy, Hydrogen Energy, electric energy, tidal energy, geothermal energy and nuclear energy etc.; though but some energy is renewable; but can not arbitraryly be utilized by the mankind, mainly be because be subjected to the restriction in space, so people have expected the exploitation of energy storage device.And as the lithium ion battery of energy accumulating device be current till the settling mode of the best of finding of people, also be the most promising scheme.Be accompanied by the increase of daily electric equipment products use amount and the universalness of power type consumer products, the demand of secondary cell also constantly increases.Lithium ion battery has just replaced later on ni-mh, NI-G to become main power supply in the portable electronics in 2000, in current power vehicle industry like a raging fire, also be the core component that can not be substituted.Anode material for lithium-ion batteries is a part very crucial in the battery industry, and its price and performance directly affect being extensive use of and promoting of lithium ion battery.
Up to the present, the commercial lithium ion battery of the overwhelming majority all is to adopt cobalt acid lithium as positive electrode.Since the resource-constrained of cobalt and costing an arm and a leg, and certain toxicity is arranged, and in charging process, cause security incidents such as burning and blast easily.Thereby people are devoted to seek other suitable substitutes always.The manganese oxide lithium has advantages such as aboundresources, pollution-free, low price, overcharging resisting are crossed and put, Heat stability is good, is considered as one of the most promising positive electrode by people.Particularly for the electrokinetic cell aspect, LiMn2O4 has tempting prospect.That research at present is maximum in the manganese oxide lithium is spinelle LiMn
2O
4, its theoretical specific capacity is 148mAh/g, and its actual capacity only is 110～120mAh/g, and voltage platform is 3.9V, and cycle performance is also not ideal enough, though this material is used in certain fields, still can not satisfy the demand of people to high-capacity battery.Can be used as the stratiform LiMnO of lithium ion anode material
2Theoretical capacity is 285mAh/g, and actual capacity can reach more than the 200mAh/g, almost is spinel-type LiMn
2O
4Two times of capacity, stratiform LiMnO
2Have the rhombus layer structure, can be Li
+Provide the three-dimensional tunnel of 3 * 3 types, Li
+At LiMnO
2In take off/embedding is than spinelle LiMn
2O
4Relatively easily, diffusion coefficient is also bigger.But stratiform LiMnO
2Difficultly directly synthesize, and in recycling process Mn
3+The Jahn-Terller distortion condition of surrounding structure causes it to change to spinel structure, causes cycle performance to descend, and irreversible capacity is big in the charge and discharge process.Discover that doping is to improve stratiform LiMnO
2Cycle performance the best way.Doping is mainly carried out modification from two kinds of approach and is reduced the Jahn-Teller effect: the one, and the metal little with atomic radiuses such as AL, Co, Ni replaces Mn, to reduce Mn
3+The Jahn-Teller effect that causes causes the contraction of structure cell, reduces Li
+Structural change when taking off embedding, stable laminated structure.The 2nd, improve monoclinic stability.After transition metal such as Nb and Ti (except the Fe) replaces Mn, be that the stability of monoclinic crystal layer structure surpasses rhombic system, monoclinic system transforms to rhombic system.
At present about the existing report of the preparation method of anode material of lithium battery layered lithium manganate, for example: Chinese patent, CN1601785 Liu Jin equality, " preparation method of positive electrode laminated cell lithium manganate of lithium ion ", its preparation process mainly comprises: two kinds of methods of hydro thermal method-calcination method are organically combined, its process route is: will mix up and contain Co, Cr, the manganese salt of Ni element and Aqueous Lithium Salts are to add in reactor at 1: 10 by solid-to-liquid ratio, in uniform temperature, pressure, carry out hydro-thermal reaction under time, reaction finishes with the liquid cooling of still internal reaction but, filter, washing, dry, in baking furnace, carry out high-temperature calcination after the drying again, promptly get the layered lithium manganate product; Chinese patent; CN1553529 Duan Xue etc.; " the oxidized inserting layer preparation method of positive electrode laminated cell lithium manganate of lithium ion ", its feature mainly comprises: manganese salt and highly basic are dissolved in the deionization that boiled the manganous hydroxide Mn (OH) that preparation has layer structure under nitrogen protection respectively
2Precursor material; Lithium compound intercalation object is joined in the lamellar precursor suspension-turbid liquid by a certain percentage, carry out intercalation and make layered lithium manganate under the synergy of oxidant, its chemical constitution formula is Li
xMnO
2(0.8≤x≤1.0) belong to rhombic system, have the Pmnm spatial symmetry, product purity height, free from admixture phase, and uniform particle diameter is controlled; Chinese patent, CN1719639 Yang Wen victory etc., " a kind of preparation method of high-lithium ion content laminated manganate cathode material for lithium ", its feature mainly comprises: the citric acid sol-gel process is adopted in invention, has the P2 structure stratiform Na of higher Na ion concentration with preparation by control Na/ (Mn+Co or Ni) rate of charge
x[Mn
1-yM
y] O
2Presoma obtains O2 structure stratiform Li by the fused salt ion-exchange reactions then
x[Mn
1-yM
y] O
2Product.
In general, layered lithium manganate is difficult directly to be synthesized, and in recycling process Mn
3+The Jahn-Teller distortion of surrounding structure causes it to change to spinel structure, causes cycle performance to descend.Adopt ion-exchange or sol-gel process, preparation process complexity, condition harshness, suitability for industrialized production be difficulty comparatively. and this patent adopts co-precipitation and ion-exchange to synthesize stratiform LiMnO
2, simple synthetic method, the preparation condition gentleness has the good industrialized productive potentialities.Simultaneously stratiform LiMnO2 is carried out doping vario-property research, made its cycle performance obtain effective raising, have both the advantage of manganese, nickel and cobalt based material, and the cost of material is low, be easy to realize suitability for industrialized production.
Summary of the invention
The objective of the invention is to propose a kind of power-type lithium ion battery stratiform manganese based composites and preparation method thereof.
For achieving the above object, the present invention is given a kind of power-type lithium ion battery is to be raw material with lithium source, manganese source, nickel source, cobalt source with stratiform manganese based composites, sodium salt is a media, and make Na: Mn: Ni: the mol ratio of Co is 1: (0.5≤x＜1.0): (0≤y≤0.5): (1-x-y), the amount that mix in the lithium source is 4～10 times of sodium salt material molal quantity.
Use in the stratiform manganese based composites technical scheme at above-mentioned power-type lithium ion battery, described lithium source is at least a in lithium chloride, lithium bromide, lithium nitrate, the lithium carbonate.
Use in the stratiform manganese based composites technical scheme at above-mentioned power-type lithium ion battery, described manganese source is at least a in manganese nitrate, manganese chloride, the manganese acetate.
Use in the stratiform manganese based composites technical scheme at above-mentioned power-type lithium ion battery, described nickel source is at least a in nickel nitrate, nickelous sulfate, nickel chloride, the nickel acetate.
Use in the stratiform manganese based composites technical scheme at above-mentioned power-type lithium ion battery, described sodium salt is at least a in natrium carbonicum calcinatum, sodium nitrate, the sodium chloride.
Use in the stratiform manganese based composites technical scheme at above-mentioned power-type lithium ion battery, described cobalt source is at least a in cobalt nitrate, cobaltous sulfate, the cobalt chloride.
For achieving the above object, the present invention gives a kind of power-type lithium ion battery preparation method with stratiform manganese based composites, and this preparation method comprises the following steps,
1) at first, take by weighing lithium source, manganese source, nickel source, cobalt source and sodium salt by a certain percentage respectively, and make Na: the mol ratio of Mn: Ni: Co is 1: (0.5≤x＜1.0): (0≤y≤0.5): (1-x-y), lithium source volume is 4～10 times of sodium salt material molal quantity;
2) will be dissolved in the water high-speed stirred and ultrasonic each 10～15min after manganese source, nickel source, the fragmentation of cobalt source employing comminution by gas stream machine.In solution, dropwise add excessive NH
3OH forms M (OH)
2Co-precipitation, M=(Mn, Ni and Co) wherein, decompress filter adopts deionized water wash to neutrality, puts into baking oven, in 50～100 ℃ of oven dry down;
3) add sodium salt by the metering ratio, adopt and fully mix 1～3h in the planetary ball mill, then mixture is put into mould, be molded into piece under pressure 5～15MPa, clamp time is 10～15min;
4) module that suppresses is packed in corundum casket body or the crucible, puts into the roasting of high frequency reactor, and temperature control technology is: heat up with 10～30 ℃/min firing rate, rise to 300～450 ℃ by room temperature, constant temperature calcining 1～20h; Heat up with 5～10 ℃/min speed again, at 600～900 ℃ of following constant temperature calcining 6～18h; Be cooled to room temperature with 30～60 ℃/min speed at last, obtain presoma stratiform Na (Mn
xNi
yCo
1-x-y) O
2
5) with presoma stratiform Na (Mn
xNi
yCo
1-x-y) O
2After putting into planetary ball mill and grinding 1～3h, join in the n-hexyl alcohol solution in the 5～10mol/L lithium source for preparing, ultrasonic and stir each 10～15min after, at 140～160 ℃ of following reflux 8～16h;
6) naturally cool to room temperature, with the mixed liquor decompress filter, sediment washs to pH value=7 with anodal pure and mild ethanol, then sample is passed through ball mill grinding again, sieves, dries, and promptly gets lithium ion battery layered lithium manganate composite L i (Mn
xNi
yCo
1-x-y) O
2
In the preparation method of above-mentioned power-type lithium ion battery with stratiform manganese based composites, be by adding sodium salt by the metering ratio, adopt and fully mix 1～3h in the planetary ball mill, then mixture being put into mould, be molded into piece under pressure 5～15MPa, clamp time is 10～15min.
In the preparation method of above-mentioned power-type lithium ion battery with stratiform manganese based composites, the module that suppresses is packed in corundum casket body or the crucible, put into the roasting of high frequency reactor, temperature control technology is: heat up with 10～30 ℃/min firing rate, rise to 300～450 ℃ by room temperature, constant temperature calcining 1～20h; Heat up with 5～10 ℃/min speed again, at 600～900 ℃ of following constant temperature calcining 6～18h; Be cooled to room temperature with 30～60 ℃/min speed at last, obtain stratiform presoma Na (Mn
xNi
yCo
1-x-y) O
2
In the preparation method of above-mentioned power-type lithium ion battery, with presoma Na (Mn with stratiform manganese based composites
xNi
yCo
1-x-y) O
2After putting into planetary ball mill and grinding 1～3h, join in the n-hexyl alcohol solution in the 5～10mol/L lithium source for preparing, ultrasonic and stir each 10～15min after, at 140～160 ℃ of following reflux 8～16h.
The invention has the beneficial effects as follows:
Adopt the given power-type lithium ion battery of the present invention with stratiform manganese based composites preparation method, raw material sources are extensive, and technology is simple and easy to control, and is pollution-free, and low cost has bigger technological design degree, are easy to realize the suitability for industrialized production that cleans.This stratiform manganese based composites preparation method adopts co-precipitation and ion-exchange process, and the uniformity that raw material is mixed improves greatly; By controlling heat treated temperature and time, the product crystal property is good, composition is even, this preparation method adopts cobalt, and nickel mixes, and compound is molded into technologies such as bulk and control sintering condition, the particle diameter and the chemical composition of layered lithium manganate composite material have been controlled effectively, the even admixture that can effectively keep raw material reduces the material diffusion in the solid phase reaction, thereby helps forming crystallinity layered lithium manganate composite material preferably; The layered lithium manganate composite material granular of this preparation method's gained is tiny, even, has good electrochemical, most importantly cycle performance, the reversible capacity that discharges and recharges all improves a lot, the products therefrom first discharge specific capacity is 200-210mAh/g, and circulating, capacity still remains on more than the 185mAh/g after 20 times.The layered lithium manganate composite material that adopts preparation method of the present invention to obtain has very high practical value, is with a wide range of applications as cell positive material.
Specific embodiment
Embodiment 1: at first, be 1: 0.8: 0.1 by the mol ratio of Na: Mn: Ni: Co: 0.1 weighing sodium carbonate, manganese nitrate, nickel acetate, cobalt chloride and lithium bromide respectively, the amount that lithium bromide mixes is 5 times of sodium carbonate material molal quantity.To be dissolved in the water after manganese nitrate, nickel acetate, the fragmentation of cobalt chloride employing comminution by gas stream machine, high-speed stirred and ultrasonic each 10min dropwise add excessive NH in solution
3OH forms M (OH)
2Co-precipitation, M=(Mn, Ni and Co) wherein, decompress filter adopts deionized water wash to neutrality, puts into baking oven, in 80 ℃ of oven dry down.Add sodium carbonate, adopt and fully mix 2h in the planetary ball mill, then mixture is put into mould, be molded into piece under pressure 10MPa, clamp time is 12min, and the module that suppresses is packed in corundum casket body or the crucible, put into the roasting of high frequency reactor, temperature control technology is: heat up with 20 ℃/min firing rate, rise to 350 ℃ by room temperature, constant temperature calcining 8h; Heat up with 10 ℃/min speed again,, be cooled to room temperature with 30 ℃/min speed at last, obtain presoma stratiform Na (Mn at 750 ℃ of following constant temperature calcining 10h
0.8Ni
0.1Co
0.1) O
2With presoma stratiform Na (Mn
0.8Ni
0.1Co
0.1) O
2After putting into planetary ball mill and grinding 1～3h, join in the n-hexyl alcohol solution of the 8mol/L lithium bromide for preparing, ultrasonic and stir each 10min after, pour in the condensation reflux unit, at 150 ℃ of following reflux 8h.Naturally cool to room temperature, with the mixed liquor decompress filter, sediment washs to pH value=7 with anodal pure and mild ethanol, then sample is passed through ball mill grinding again, sieves, dries, and promptly gets the layered lithium manganate composite L i (Mn that lithium ion battery is used
0.8Ni
0.1Co
0.1) O
2The products therefrom first discharge specific capacity is 208mAh/g, and circulating, capacity still remains on more than the 187mAh/g after 20 times.
Embodiment 2: at first, be 1: 0.6: 0.2 by the mol ratio of Na: Mn: Ni: Co: 0.2 takes by weighing natrium carbonicum calcinatum, manganese nitrate, nickel acetate, cobaltous sulfate and lithium nitrate respectively, and the amount that lithium nitrate mixes is 8 times of natrium carbonicum calcinatum material molal quantity.To be dissolved in the water after manganese nitrate, nickel acetate, the fragmentation of cobaltous sulfate employing comminution by gas stream machine, high-speed stirred and ultrasonic each 15min dropwise add excessive NH in solution
3OH forms M (OH)
2Co-precipitation, M=(Mn, Ni and Co) wherein, decompress filter adopts deionized water wash to neutrality, puts into baking oven, in 70 ℃ of oven dry down.Add natrium carbonicum calcinatum, adopt and fully mix 3h in the planetary ball mill, then mixture is put into mould, be molded into piece under pressure 15MPa, clamp time is 15min; The module that suppresses is packed in corundum casket body or the crucible, puts into the roasting of high frequency reactor, and temperature control technology is: heat up with 15 ℃/min firing rate, rise to 400 ℃ by room temperature, constant temperature calcining 15h; Heat up with 10 ℃/min speed again,, be cooled to room temperature with 50 ℃/min speed at last, obtain presoma stratiform Na (Mn at 700 ℃ of following constant temperature calcining 12h
0.6Ni
0.2Co
0.2) O
2With presoma stratiform Na (Mn
0.6Ni
0.2Co
0.2) O
2After putting into planetary ball mill and grinding 1.5h, join in the n-hexyl alcohol solution of the 8mol/L lithium nitrate for preparing, ultrasonic and stir each 15min after, pour in the condensation reflux unit, at 150 ℃ of following reflux 15h.Naturally cool to room temperature, with the mixed liquor decompress filter, sediment washs to pH value=7 with anodal pure and mild ethanol, then sample is passed through ball mill grinding again, sieves, dries, and promptly gets the layered lithium manganate composite L i (Mn that lithium ion battery is used
0.6Ni
0.2Co
0.2) O
2The products therefrom first discharge specific capacity is 200mAh/g, and circulating, capacity still remains on more than the 189mAh/g after 20 times.
Embodiment 3: at first, be 1: 0.7: 0.2 by the mol ratio of Na: Mn: Ni: Co: 0.1 takes by weighing sodium chloride, manganese nitrate, nickelous sulfate, cobaltous sulfate and lithium bromide respectively, and the amount that lithium bromide mixes is 8 times of sodium chloride material molal quantity.To be dissolved in the water after manganese nitrate, nickelous sulfate, the fragmentation of cobaltous sulfate employing comminution by gas stream machine, high-speed stirred and ultrasonic each 12min dropwise add excessive NH in solution
3OH forms M (OH)
2Co-precipitation, M=(Mn, Ni and Co) wherein, decompress filter adopts deionized water wash to neutrality, puts into baking oven, in 90 ℃ of oven dry down.Add sodium chloride, adopt and fully mix 3h in the planetary ball mill, then mixture is put into mould, be molded into piece under pressure 15MPa, clamp time is 10min; The module that suppresses is packed in corundum casket body or the crucible, puts into the roasting of high frequency reactor, and temperature control technology is: heat up with 10 ℃/min firing rate, rise to 450 ℃ by room temperature, constant temperature calcining 8h; Heat up with 10 ℃/min speed again,, be cooled to room temperature with 40 ℃/min speed at last, obtain presoma stratiform Na (Mn at 800 ℃ of following constant temperature calcining 10h
0.7Ni
0.2Co
0.1) O
2With presoma stratiform Na (Mn
0.7Ni
0.2Co
0.1) O
2After putting into planetary ball mill and grinding 1～3h, join in the n-hexyl alcohol solution of the 5～10mol/L lithium bromide for preparing, ultrasonic and stir each 10～15min after, pour in the condensation reflux unit, at 145 ℃ of following reflux 10h.Naturally cool to room temperature, with the mixed liquor decompress filter, sediment washs to pH value=7 with anodal pure and mild ethanol, then sample is passed through ball mill grinding again, sieves, dries, and promptly gets the layered lithium manganate composite L i (Mn that lithium ion battery is used
0.7Ni
0.2Co
0.1) O
2The products therefrom first discharge specific capacity is 210mAh/g, and circulating, capacity still remains on more than the 185mAh/g after 20 times.
Embodiment 4: at first, be 1: 0.6: 0.2 by the mol ratio of Na: Mn: Ni: Co: 0.2 takes by weighing sodium chloride, manganese acetate, nickel chloride, cobalt nitrate and lithium chloride respectively, and the amount that lithium chloride mixes is 10 times of sodium chloride material molal quantity.To be dissolved in the water after manganese acetate, nickel chloride, the fragmentation of cobalt nitrate employing comminution by gas stream machine, high-speed stirred and ultrasonic each 15min dropwise add excessive NH in solution
3OH forms M (OH)
2Co-precipitation, M=(Mn, Ni and Co) wherein, decompress filter adopts deionized water wash to neutrality, puts into baking oven, in 70 ℃ of oven dry down.Add sodium chloride, adopt and fully mix 3h in the planetary ball mill, then mixture is put into mould, be molded into piece under pressure 8MPa, clamp time is 10min; The module that suppresses is packed in corundum casket body or the crucible, puts into the roasting of high frequency reactor, and temperature control technology is: heat up with 10 ℃/min firing rate, rise to 350 ℃ by room temperature, constant temperature calcining 15h; Heat up with 10 ℃/min speed again,, be cooled to room temperature with 50 ℃/min speed at last, obtain presoma stratiform Na (Mn at 900 ℃ of following constant temperature calcining 10h
0.6Ni
0.2Co
0.2) O
2With presoma stratiform Na (Mn
0.6Ni
0.2Co
0.2) O
2After putting into planetary ball mill and grinding 2h, join in the n-hexyl alcohol solution of the 10mol/L lithium chloride for preparing, ultrasonic and stir each 8min after, pour in the condensation reflux unit, at 155 ℃ of following reflux 15h.Naturally cool to room temperature, with the mixed liquor decompress filter, sediment washs to pH value=7 with anodal pure and mild ethanol, then sample is passed through ball mill grinding again, sieves, dries, and promptly gets the layered lithium manganate composite L i (Mn that lithium ion battery is used
0.6Ni
0.2Co
0.2) O
2The products therefrom first discharge specific capacity is 208mAh/g, and circulating, capacity still remains on more than the 189mAh/g after 20 times.
Claims (10)
1. a power-type lithium ion battery is with stratiform manganese base composite L i (Mn
xNi
yCo
1-x-y) O
2, it is characterized in that: described power-type lithium ion battery stratiform manganese base composite L i (Mn
xNi
yCo
1-x-y) O
2Be to be raw material with lithium source, manganese source, nickel source, cobalt source, sodium salt is a media, and makes Na: the mol ratio of Mn: Ni: Co is 1: (0.5≤x＜1.0): (0≤y≤0.5): (1-x-y), the amount that mix in the lithium source is 4～10 times of sodium salt material molal quantity.
2. a kind of power-type lithium ion battery according to claim 1 layered lithium manganate composite L i (Mn
xNi
yCo
1-x-y) O
2, it is characterized in that: described lithium source is at least a in lithium chloride, lithium bromide, lithium nitrate, the lithium carbonate.
3. a kind of power-type lithium ion battery according to claim 1 stratiform manganese base composite L i (Mn
xNi
yCo
1-x-y) O
2, it is characterized in that: described manganese source is at least a in manganese nitrate, manganese chloride, the manganese acetate.
4. a kind of power-type lithium ion battery according to claim 1 stratiform manganese base composite L i (Mn
xNi
yCo
1-x-y) O
2, it is characterized in that: described nickel source is at least a in nickel nitrate, nickelous sulfate, nickel chloride, the nickel acetate.
5. a kind of power-type lithium ion battery according to claim 1 stratiform manganese base composite L i (Mn
xNi
yCo
1-x-y) O
2, it is characterized in that: described cobalt source is at least a in cobalt nitrate, cobaltous sulfate, the cobalt chloride.
6. a kind of power-type lithium ion battery according to claim 1 stratiform manganese base composite L i (Mn
xNi
yCo
1-x-y) O
2, it is characterized in that: described sodium salt is at least a in natrium carbonicum calcinatum, sodium nitrate, the sodium chloride
7. a power-type lithium ion battery is with stratiform manganese base composite L i (Mn
xNi
yCo
1-x-y) O
2The preparation method, it is characterized in that: this preparation method comprises the following steps,
1) at first, take by weighing lithium source, manganese source, nickel source, cobalt source and sodium salt by a certain percentage respectively, and make Na: Mn: Ni: the mol ratio of Co is 1: (0.5≤x＜1.0): (0≤y≤0.5): (1-x-y), the amount that mix in the lithium source is 4～10 times of sodium salt material molal quantity;
2) will be dissolved in the water after manganese source, nickel source, the fragmentation of cobalt source employing comminution by gas stream machine, high-speed stirred and ultrasonic each 10～15min dropwise add excessive NH in solution
4OH forms M (OH)
2Co-precipitation, M=(Mn, Ni and Co) wherein, decompress filter adopts deionized water wash to neutrality, puts into baking oven, in 50～100 ℃ of oven dry down;
3) add sodium salt by the metering ratio, adopt and fully mix 1～3h in the planetary ball mill, then mixture is put into mould, be molded into piece under pressure 5～15MPa, clamp time is 10～15min;
4) module that suppresses is packed in corundum casket body or the crucible, puts into the roasting of high frequency reactor, and temperature control technology is: heat up with 10～30 ℃/min firing rate, rise to 300～450 ℃ by room temperature, constant temperature calcining 1～20h; Heat up with 5～10 ℃/min speed again, at 600～900 ℃ of following constant temperature calcining 6～18h; Be cooled to room temperature with 30～60 ℃/min speed at last, obtain presoma stratiform Na (Mn
xNi
yCo
1-x-y) O
2
5) with presoma stratiform Na (Mn
xNi
yCo
1-x-y) O
2After putting into planetary ball mill and grinding 1～3h, join in the n-hexyl alcohol solution in the 5～10mol/L lithium source for preparing, ultrasonic and stir each 10～15min after, at 140～160 ℃ of following reflux 8～16h;
6) naturally cool to room temperature, with the mixed liquor decompress filter, sediment washs to pH value=7 with anodal pure and mild ethanol, then sample is passed through ball mill grinding again, sieves, dries, and promptly gets the stratiform manganese base composite L i (Mn that lithium ion battery is used
xNi
yCo
1-x-y) O
2
8. a kind of power-type lithium ion battery according to claim 7 stratiform Li (Mn
xNi
yCo
1-x-y) O
2The preparation method of composite material is characterized in that:, adopt and fully mix 1～3h in the planetary ball mill than adding sodium salt by metering, then mixture is put into mould, be molded into piece under pressure 5～15MPa, clamp time is 10～15min.
9. a kind of power-type lithium ion battery according to claim 7 stratiform Li (Mn
xNi
yCo
1-x-y) O
2The preparation method of composite material, it is characterized in that: the module that suppresses is packed in corundum casket body or the crucible, puts into the roasting of high frequency reactor, and temperature control technology is: heat up with 10～30 ℃/min firing rate, rise to 300～450 ℃ by room temperature, constant temperature calcining 1～20h; Heat up with 5～10 ℃/min speed again, at 600～900 ℃ of following constant temperature calcining 6～18h; Be cooled to room temperature with 30～60 ℃/min speed at last, obtain stratiform presoma Na (Mn
xNi
yCo
1-x-y) O
2
10. a kind of power-type lithium ion battery according to claim 7 stratiform Li (Mn
xNi
yCo
1-x-y) O
2The preparation method of composite material is characterized in that: with presoma Na (Mn
xNi
yCo
1-x-y) O
2After putting into planetary ball mill and grinding 1～3h, join in the n-hexyl alcohol solution in the 5～10mol/L lithium source for preparing, ultrasonic and stir each 10～15min after, at 140～160 ℃ of following reflux 8～16h.
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| CN109395647A (en) * | 2018-11-19 | 2019-03-01 | 宁波富理电池材料科技有限公司 | A kind of double ultrasound couple devices and the method for preparing lithium-rich manganese-based anode material presoma and its positive electrode |
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| CN113644274A (en) * | 2021-09-15 | 2021-11-12 | 广州大学 | O2 type lithium ion battery anode material and preparation method and application thereof |
| CN113644274B (en) * | 2021-09-15 | 2022-11-01 | 广州大学 | O2 type lithium ion battery anode material and preparation method and application thereof |
| CN114436345A (en) * | 2022-02-14 | 2022-05-06 | 中南大学 | Ternary cathode material of lithium ion battery and preparation method thereof |
| CN114436345B (en) * | 2022-02-14 | 2022-11-11 | 中南大学 | Ternary cathode material of lithium ion battery and preparation method thereof |
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| CN114447309B (en) * | 2022-02-15 | 2023-11-10 | 中南大学 | Sodium ion doped lithium ion battery positive electrode material and preparation method thereof |
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