CN102255083B - 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
- Publication number
- CN102255083B CN102255083B CN201010530997.3A CN201010530997A CN102255083B CN 102255083 B CN102255083 B CN 102255083B CN 201010530997 A CN201010530997 A CN 201010530997A CN 102255083 B CN102255083 B CN 102255083B
- Authority
- CN
- China
- Prior art keywords
- source
- lithium
- manganese
- preparation
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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)
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 layered manganese-based composite material 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 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.; although but some energy is renewable; but can not arbitraryly be utilized by the mankind, be mainly that therefore people have expected the exploitation of energy storage device because be subject to the restriction in space.And as the lithium ion battery of energy accumulating device be current till the best settling mode that finds of people, be also 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 ni-mh, NI-G to become the main power source in portable electronics after 2000, in current power vehicle industry like a raging fire, is also the core component can not be substituted.Anode material for lithium-ion batteries is part very crucial in battery industry, and its price and performance directly affect being widely used and promoting of lithium ion battery.
Up to the present, the overwhelming majority commercial lithium ion battery be all to adopt cobalt acid lithium as positive electrode.Due to the resource-constrained of cobalt and expensive, and there is certain toxicity, and in charging process, easily cause the security incidents such as burning and blast.Thereby people are devoted to find other suitable substitutes always.Manganese oxide lithium has the 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 electrokinetic cell aspect, LiMn2O4 has tempting prospect.In manganese oxide lithium, that current most study is spinelle LiMn
2o
4, its theoretical specific capacity is 148mAh/g, and its actual capacity is only 110～120mAh/g, and voltage platform is 3.9V, and cycle performance is also not ideal enough, although this material is in certain fields application, still can not meet 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, more than actual capacity can reach 200mAh/g, is almost spinel-type LiMn
2o
4two times of capacity, stratiform LiMnO
2there is rhombus layer structure, can be Li
+provide the three-dimensional tunnel of 3 × 3 types, Li
+at LiMnO
2in de-/embedding than spinelle LiMn
2o
4relatively easily, diffusion coefficient is also larger.But stratiform LiMnO
2more difficult directly synthetic, and recycling Mn in process
3+the Jahn-Terller distortion condition of surrounding structure causes it to change to spinel structure, causes cycle performance to decline, and in charge and discharge process, irreversible capacity is large.Research discovery, 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 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 causing, causes the contraction of structure cell, reduces Li
+structural change when deintercalation, stable laminated structure.The 2nd, improve monoclinic stability.The transition metal such as Nb and Ti (except Fe) replaces after Mn, is that the stability of monoclinic crystal layer structure exceedes rhombic system, and monoclinic system transforms to rhombic system.
Have been reported about the preparation method of anode material of lithium battery layered lithium manganate at present, 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 at 1: 10 in reactor by solid-to-liquid ratio, in uniform temperature, pressure, under time, carry out hydro-thermal reaction, react complete by cooling reactant liquor in still, filter, washing, dry, after dry, in baking furnace, carry out again high-temperature calcination, obtain 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 respectively in the deionization boiling under nitrogen protection, and preparation has the manganous hydroxide Mn (OH) of layer structure
2precursor material, lithium compound intercalation object is joined in 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 Pmnm spatial symmetry, and product purity is high, 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: invention adopts citric acid sol-gel method method, has the P2 structure stratiform Na of higher Na ion concentration by controlling Na/ (Mn+Co or Ni) rate of charge with preparation
x[Mn
1-ym
y] O
2presoma, then obtains O2 structure stratiform Li by fused salt ion-exchange reactions
x[Mn
1-ym
y] O
2product.
In general, layered lithium manganate is more difficult directly synthetic, and recycling Mn in process
3+the Jahn-Teller distortion of surrounding structure causes it to change to spinel structure, causes cycle performance to decline.Adopt ion-exchange or sol-gel process, preparation process complexity, condition harshness, suitability for industrialized production is difficulty comparatively. and this patent adopts co-precipitation and ion-exchange to synthesize stratiform LiMnO
2, simple synthetic method, preparation condition gentleness, has good suitability for industrialized production potentiality.Stratiform LiMnO2 is carried out to doping vario-property research simultaneously, 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 object of the invention is to propose a kind of power-type lithium ion battery layered manganese-based composite material and preparation method thereof.
For achieving the above object, the present invention is given, and a kind of power-type lithium ion battery layered manganese-based composite material is take lithium source, manganese source, nickel source, cobalt source be as raw material, sodium salt is medium, 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 lithium source is 4～10 times of sodium salt material molal quantity.
At above-mentioned power-type lithium ion battery, with in layered manganese-based composite material technical scheme, described lithium source is at least one in lithium chloride, lithium bromide, lithium nitrate, lithium carbonate.
At above-mentioned power-type lithium ion battery, with in layered manganese-based composite material technical scheme, described manganese source is at least one in manganese nitrate, manganese chloride, manganese acetate.
At above-mentioned power-type lithium ion battery, with in layered manganese-based composite material technical scheme, described nickel source is at least one in nickel nitrate, nickelous sulfate, nickel chloride, nickel acetate.
At above-mentioned power-type lithium ion battery, with in layered manganese-based composite material technical scheme, described sodium salt is at least one in natrium carbonicum calcinatum, sodium nitrate, sodium chloride.
At above-mentioned power-type lithium ion battery, with in layered manganese-based composite material technical scheme, described cobalt source is at least one in cobalt nitrate, cobaltous sulfate, cobalt chloride.
For achieving the above object, the present invention gives the preparation method of a kind of power-type lithium ion battery layered manganese-based composite material, and this preparation method comprises the following steps,
1) first, take respectively by a certain percentage lithium source, manganese source, nickel source, cobalt source and sodium salt, and make Na: Mn: Ni: the mol ratio of 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 after manganese source, nickel source, the fragmentation of cobalt source employing air-flow crushing machine, be dissolved in water high-speed stirred and ultrasonic each 10～15min.In solution, dropwise add excessive NH
3oH, forms M (OH)
2co-precipitation, wherein M=(Mn, Ni and Co), decompress filter, adopts deionized water to wash to neutrality, puts into baking oven, at 50～100 ℃, dries;
3) by measuring than adding sodium salt, adopt in planetary ball mill and fully mix 1～3h, then mixture is put into mould, under pressure 5～15MPa, be molded into piece, clamp time is 10～15min;
4) module suppressing packs in corundum casket body or crucible, puts into the roasting of high frequency reactor, and temperature control technique is: heat up with 10～30 ℃/min firing rate, rise to 300～450 ℃, constant temperature calcining 1～20h by room temperature; Heat up with 5～10 ℃/min speed again, constant temperature calcining 6～18h at 600～900 ℃; Finally be cooled to room temperature with 30～60 ℃/min speed, obtain presoma stratiform Na (Mn
xni
yco
1-x-y) O
2;
5) by presoma stratiform Na (Mn
xni
yco
1-x-y) O
2put into planetary ball mill and grind after 1～3h, join in the n-hexyl alcohol solution in the 5～10mol/L lithium source preparing, ultrasonic and stir after each 10～15min, at 140～160 ℃, add hot reflux 8～16h;
6) naturally cool to room temperature, by mixed liquor decompress filter, sediment washs to pH value=7 with anodal alcohol and ethanol, then sample is passed through to ball mill grinding again, sieves, dries, and obtains lithium ion battery layered lithium manganate composite L i (Mn
xni
yco
1-x-y) O
2.
Use in the preparation method of layered manganese-based composite material at above-mentioned power-type lithium ion battery, be by by measuring than adding sodium salt, adopt in planetary ball mill and fully mix 1～3h, then mixture is put into mould, under pressure 5～15MPa, be molded into piece, clamp time is 10～15min.
Use in the preparation method of layered manganese-based composite material at above-mentioned power-type lithium ion battery, the module suppressing packs in corundum casket body or crucible, put into the roasting of high frequency reactor, temperature control technique 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, constant temperature calcining 6～18h at 600～900 ℃; Finally be cooled to room temperature with 30～60 ℃/min speed, obtain stratiform presoma Na (Mn
xni
yco
1-x-y) O
2.
Use in the preparation method of layered manganese-based composite material, by presoma Na (Mn at above-mentioned power-type lithium ion battery
xni
yco
1-x-y) O
2put into planetary ball mill and grind after 1～3h, join in the n-hexyl alcohol solution in the 5～10mol/L lithium source preparing, ultrasonic and stir after each 10～15min, at 140～160 ℃, add hot reflux 8～16h.
The invention has the beneficial effects as follows:
Adopt the given power-type lithium ion battery of the present invention layered manganese-based composite material preparation method, raw material sources are extensive, and technique is simple and easy to control, pollution-free, and low cost has larger technological design degree, is easy to realize clean suitability for industrialized production.This layered manganese-based composite material preparation method adopts co-precipitation and ion-exchange process, and the uniformity that can make raw material mix improves greatly; By controlling heat treated temperature and time, product crystal property is good, composition is even, this preparation method adopts cobalt, nickel doping, and compound is molded into bulk and controls the techniques such as sintering condition, particle diameter and the chemical composition of layered lithium manganate composite material are effectively controlled, can effectively keep the even admixture of raw material, reduce the material diffusion in solid phase reaction, thereby be conducive to form the good layered lithium manganate composite material of crystallinity; The layered lithium manganate composite material granular of this preparation method's gained is tiny, even, there is good chemical property, most importantly cycle performance, the reversible capacity discharging and recharging all improves a lot, products therefrom first discharge specific capacity is 200-210mAh/g, circulates after 20 times more than capacity still remains on 185mAh/g.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: first, be 1: 0.8: 0.1 by the mol ratio of Na: Mn: Ni: Co: 0.1 difference weighing sodium carbonate, manganese nitrate, nickel acetate, cobalt chloride and lithium bromide, the amount that lithium bromide mixes is 5 times of sodium carbonate material molal quantity.After manganese nitrate, nickel acetate, cobalt chloride are adopted to the fragmentation of air-flow crushing machine, be dissolved in water, high-speed stirred and ultrasonic each 10min dropwise add excessive NH in solution
3oH, forms M (OH)
2co-precipitation, wherein M=(Mn, Ni and Co), decompress filter, adopts deionized water to wash to neutrality, puts into baking oven, at 80 ℃, dries.Add sodium carbonate, adopt the abundant 2h of mixing in planetary ball mill, then mixture is put into mould, under pressure 10MPa, be molded into piece, clamp time is 12min, and the module suppressing packs in corundum casket body or crucible, put into the roasting of high frequency reactor, temperature control technique is: heat up with 20 ℃/min firing rate, rise to 350 ℃, constant temperature calcining 8h by room temperature; Heat up with 10 ℃/min speed, constant temperature calcining 10h at 750 ℃, is finally cooled to room temperature with 30 ℃/min speed, obtains presoma stratiform Na (Mn again
0.8ni
0.1co
0.1) O
2.By presoma stratiform Na (Mn
0.8ni
0.1co
0.1) O
2put into planetary ball mill and grind after 1～3h, join in the n-hexyl alcohol solution of the 8mol/L lithium bromide preparing, ultrasonic and stir after each 10min, pour in condensation reflux unit, at 150 ℃, add hot reflux 8h.Naturally cool to room temperature, by mixed liquor decompress filter, sediment washs to pH value=7 with anodal alcohol and ethanol, then sample is passed through to ball mill grinding again, sieves, dries, and obtains the layered lithium manganate composite L i (Mn that lithium ion battery is used
0.8ni
0.1co
0.1) O
2.Products therefrom first discharge specific capacity is 208mAh/g, circulates after 20 times more than capacity still remains on 187mAh/g.
Embodiment 2: first, be 1: 0.6: 0.2 by the mol ratio of Na: Mn: Ni: Co: 0.2 takes respectively natrium carbonicum calcinatum, manganese nitrate, nickel acetate, cobaltous sulfate and lithium nitrate, the amount that lithium nitrate mixes is 8 times of natrium carbonicum calcinatum material molal quantity.After manganese nitrate, nickel acetate, cobaltous sulfate are adopted to the fragmentation of air-flow crushing machine, be dissolved in water, high-speed stirred and ultrasonic each 15min dropwise add excessive NH in solution
3oH, forms M (OH)
2co-precipitation, wherein M=(Mn, Ni and Co), decompress filter, adopts deionized water to wash to neutrality, puts into baking oven, at 70 ℃, dries.Add natrium carbonicum calcinatum, adopt in planetary ball mill and fully mix 3h, then mixture is put into mould, under pressure 15MPa, be molded into piece, clamp time is 15min; The module suppressing packs in corundum casket body or crucible, puts into the roasting of high frequency reactor, and temperature control technique is: heat up with 15 ℃/min firing rate, rise to 400 ℃, constant temperature calcining 15h by room temperature; Heat up with 10 ℃/min speed, constant temperature calcining 12h at 700 ℃, is finally cooled to room temperature with 50 ℃/min speed, obtains presoma stratiform Na (Mn again
0.6ni
0.2co
0.2) O
2.By presoma stratiform Na (Mn
0.6ni
0.2co
0.2) O
2put into planetary ball mill and grind after 1.5h, join in the n-hexyl alcohol solution of the 8mol/L lithium nitrate preparing, ultrasonic and stir after each 15min, pour in condensation reflux unit, at 150 ℃, add hot reflux 15h.Naturally cool to room temperature, by mixed liquor decompress filter, sediment washs to pH value=7 with anodal alcohol and ethanol, then sample is passed through to ball mill grinding again, sieves, dries, and obtains the layered lithium manganate composite L i (Mn that lithium ion battery is used
0.6ni
0.2co
0.2) O
2.Products therefrom first discharge specific capacity is 200mAh/g, circulates after 20 times more than capacity still remains on 189mAh/g.
Embodiment 3: first, be 1: 0.7: 0.2 by the mol ratio of Na: Mn: Ni: Co: 0.1 takes respectively sodium chloride, manganese nitrate, nickelous sulfate, cobaltous sulfate and lithium bromide, the amount that lithium bromide mixes is 8 times of sodium chloride material molal quantity.After manganese nitrate, nickelous sulfate, cobaltous sulfate are adopted to the fragmentation of air-flow crushing machine, be dissolved in water, high-speed stirred and ultrasonic each 12min dropwise add excessive NH in solution
3oH, forms M (OH)
2co-precipitation, wherein M=(Mn, Ni and Co), decompress filter, adopts deionized water to wash to neutrality, puts into baking oven, at 90 ℃, dries.Add sodium chloride, adopt in planetary ball mill and fully mix 3h, then mixture is put into mould, under pressure 15MPa, be molded into piece, clamp time is 10min; The module suppressing packs in corundum casket body or crucible, puts into the roasting of high frequency reactor, and temperature control technique is: heat up with 10 ℃/min firing rate, rise to 450 ℃, constant temperature calcining 8h by room temperature; Heat up with 10 ℃/min speed, constant temperature calcining 10h at 800 ℃, is finally cooled to room temperature with 40 ℃/min speed, obtains presoma stratiform Na (Mn again
0.7ni
0.2co
0.1) O
2.By presoma stratiform Na (Mn
0.7ni
0.2co
0.1) O
2put into planetary ball mill and grind after 1～3h, join in the n-hexyl alcohol solution of the 5～10mol/L lithium bromide preparing, ultrasonic and stir after each 10～15min, pour in condensation reflux unit, at 145 ℃, add hot reflux 10h.Naturally cool to room temperature, by mixed liquor decompress filter, sediment washs to pH value=7 with anodal alcohol and ethanol, then sample is passed through to ball mill grinding again, sieves, dries, and obtains the layered lithium manganate composite L i (Mn that lithium ion battery is used
0.7ni
0.2co
0.1) O
2.Products therefrom first discharge specific capacity is 210mAh/g, circulates after 20 times more than capacity still remains on 185mAh/g.
Embodiment 4: first, be 1: 0.6: 0.2 by the mol ratio of Na: Mn: Ni: Co: 0.2 takes respectively sodium chloride, manganese acetate, nickel chloride, cobalt nitrate and lithium chloride, the amount that lithium chloride mixes is 10 times of sodium chloride material molal quantity.After manganese acetate, nickel chloride, cobalt nitrate are adopted to the fragmentation of air-flow crushing machine, be dissolved in water, high-speed stirred and ultrasonic each 15min dropwise add excessive NH in solution
3oH, forms M (OH)
2co-precipitation, wherein M=(Mn, Ni and Co), decompress filter, adopts deionized water to wash to neutrality, puts into baking oven, at 70 ℃, dries.Add sodium chloride, adopt in planetary ball mill and fully mix 3h, then mixture is put into mould, under pressure 8MPa, be molded into piece, clamp time is 10min; The module suppressing packs in corundum casket body or crucible, puts into the roasting of high frequency reactor, and temperature control technique is: heat up with 10 ℃/min firing rate, rise to 350 ℃, constant temperature calcining 15h by room temperature; Heat up with 10 ℃/min speed, constant temperature calcining 10h at 900 ℃, is finally cooled to room temperature with 50 ℃/min speed, obtains presoma stratiform Na (Mn again
0.6ni
0.2co
0.2) O
2.By presoma stratiform Na (Mn
0.6ni
0.2co
0.2) O
2put into planetary ball mill and grind after 2h, join in the n-hexyl alcohol solution of the 10mol/L lithium chloride preparing, ultrasonic and stir after each 8min, pour in condensation reflux unit, at 155 ℃, add hot reflux 15h.Naturally cool to room temperature, by mixed liquor decompress filter, sediment washs to pH value=7 with anodal alcohol and ethanol, then sample is passed through to ball mill grinding again, sieves, dries, and obtains the layered lithium manganate composite L i (Mn that lithium ion battery is used
0.6ni
0.2co
0.2) O
2.Products therefrom first discharge specific capacity is 208mAh/g, circulates after 20 times more than capacity still remains on 189mAh/g.
Claims (6)
1. a layered manganese-based composite material Li (Mn
xni
yco
1-x-y) O
2preparation method, it is characterized in that: this preparation method comprises the following steps,
1) first, take respectively by a certain percentage lithium source, manganese source, nickel source, cobalt source and sodium salt, and the mol ratio that makes Na:Mn:Ni:Co is 1:(0.5≤x<1.0): (0≤y≤0.5): (1-x-y), the amount that mix in lithium source is 4～10 times of sodium salt material molal quantity;
2) will after manganese source, nickel source, the fragmentation of cobalt source employing air-flow crushing machine, be dissolved in water, high-speed stirred and ultrasonic each 10～15min dropwise add excessive NH in solution
4oH, forms M (OH)
2co-precipitation, wherein M=(Mn, Ni and Co), decompress filter, adopts deionized water to wash to neutrality, puts into baking oven, at 50～100 ℃, dries;
3) by measuring than adding sodium salt, adopt in planetary ball mill and fully mix 1～3h, then mixture is put into mould, under pressure 5～15MPa, be molded into piece, clamp time is 10～15min;
4) module suppressing packs in corundum casket body or crucible, puts into the roasting of high frequency reactor, and temperature control technique is: heat up with 10～30 ℃/min firing rate, rise to 300～450 ℃, constant temperature calcining 1～20h by room temperature; Heat up with 5～10 ℃/min speed again, constant temperature calcining 6～18h at 600～900 ℃; Finally be cooled to room temperature with 30～60 ℃/min speed, obtain presoma stratiform Na (Mn
xni
yco
1-x-y) O
2;
5) by presoma stratiform Na (Mn
xni
yco
1-x-y) O
2put into planetary ball mill and grind after 1～3h, join in the n-hexyl alcohol solution in the 5～10mol/L lithium source preparing, ultrasonic and stir after each 10～15min, at 140～160 ℃, add hot reflux 8～16h;
6) naturally cool to room temperature, by mixed liquor decompress filter, sediment washs to pH value=7 with anodal alcohol and ethanol, then sample is passed through to ball mill grinding again, sieves, dries, and obtains the layered manganese-based composite material Li (Mn that lithium ion battery is used
xni
yco
1-x-y) O
2.
2. a kind of stratiform Li (Mn according to claim 1
xni
yco
1-x-y) O
2the preparation method of composite material, is characterized in that: described lithium source is at least one in lithium chloride, lithium bromide, lithium nitrate, lithium carbonate.
3. a kind of stratiform Li (Mn according to claim 1
xni
yco
1-x-y) O
2the preparation method of composite material, is characterized in that: described manganese source is at least one in manganese nitrate, manganese chloride, manganese acetate.
4. a kind of stratiform Li (Mn according to claim 1
xni
yco
1-x-y) O
2the preparation method of composite material, is characterized in that: described nickel source is at least one in nickel nitrate, nickelous sulfate, nickel chloride, nickel acetate.
5. a kind of stratiform Li (Mn according to claim 1
xni
yco
1-x-y) O
2the preparation method of composite material, is characterized in that: described cobalt source is at least one in cobalt nitrate, cobaltous sulfate, cobalt chloride.
6. a kind of stratiform Li (Mn according to claim 1
xni
yco
1-x-y) O
2the preparation method of composite material, is characterized in that: described sodium salt is at least one in natrium carbonicum calcinatum, sodium nitrate, sodium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010530997.3A CN102255083B (en) | 2010-11-04 | 2010-11-04 | Layered manganese-based composite material for power-type lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010530997.3A CN102255083B (en) | 2010-11-04 | 2010-11-04 | Layered manganese-based composite material for power-type lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102255083A CN102255083A (en) | 2011-11-23 |
| CN102255083B true CN102255083B (en) | 2014-05-21 |
Family
ID=44982178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010530997.3A Expired - Fee Related CN102255083B (en) | 2010-11-04 | 2010-11-04 | Layered manganese-based composite material for power-type lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102255083B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101944238B1 (en) * | 2011-12-08 | 2019-01-31 | 바스프 에스이 | Electrochemical cells and the use thereof |
| JP6066306B2 (en) * | 2012-07-04 | 2017-01-25 | 株式会社Ｇｓユアサ | Non-aqueous electrolyte secondary battery and method for producing non-aqueous electrolyte secondary battery |
| CN105390666B (en) * | 2015-12-24 | 2018-09-11 | 哈尔滨工业大学 | A kind of mixed lithium method in lithium ion anode material building-up process |
| 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 |
| CN111180722B (en) * | 2020-01-08 | 2022-09-27 | 太原理工大学 | Preparation method of lithium ion battery anode material nickel cobalt lithium aluminate |
| 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 |
| CN114436345B (en) * | 2022-02-14 | 2022-11-11 | 中南大学 | Ternary cathode material of lithium ion battery and preparation method thereof |
| 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 |
| CN115050935A (en) * | 2022-06-09 | 2022-09-13 | 广州大学 | Layered high-nickel ternary lithium ion battery positive electrode material, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101257134A (en) * | 2007-03-01 | 2008-09-03 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| CN101740773A (en) * | 2009-12-22 | 2010-06-16 | 江苏环能通环保科技有限公司 | Lithium battery cathode material with manganese-based layered-crystal structure and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1719639A (en) * | 2005-05-13 | 2006-01-11 | 北京化工大学 | Method ofr prpearing high-lithium ion content laminated lithium manganate anode material |
| CN101453014B (en) * | 2007-12-06 | 2011-08-31 | 黄炳照 | Production method for electrode material of battery |
-
2010
- 2010-11-04 CN CN201010530997.3A patent/CN102255083B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101257134A (en) * | 2007-03-01 | 2008-09-03 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| CN101740773A (en) * | 2009-12-22 | 2010-06-16 | 江苏环能通环保科技有限公司 | Lithium battery cathode material with manganese-based layered-crystal structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102255083A (en) | 2011-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102255083B (en) | Layered manganese-based composite material for power-type lithium ion battery and preparation method thereof | |
| CN103441252B (en) | The preparation method of nano-oxide coated lithium ion battery lithium-rich manganese-based anode material | |
| CN102881891B (en) | Method for preparing trivalent ion-doped lithium-rich solid solution cathode material | |
| CN102244237B (en) | A kind of synthetic method of anode material for lithium ion battery with high power capacity | |
| CN107437619A (en) | A kind of anode for lithium battery material and preparation method thereof | |
| CN102201573A (en) | Rich-lithium positive electrode material of lithium ion battery having coreshell structure and preparation method of rich-lithium positive electrode material | |
| CN106299352A (en) | The preparation method of positive pole material of secondary lithium battery | |
| CN102623691B (en) | Method for preparing lithium nickel manganese oxide serving as cathode material of lithium battery | |
| CN102332585A (en) | Lithium nickel cobalt manganese oxygen/stannic oxide composite anode material doped with metal elements and method for preparing lithium nickel cobalt manganese oxygen/stannic oxide composite anode material | |
| CN103606663B (en) | A kind of Multiplying-power lithium-rich composite anode material and preparation method thereof | |
| CN104134797B (en) | A kind of high-capacity lithium-rich cathode material and preparation method thereof | |
| CN103606667A (en) | Preparation method for manganese solid solution anode material of lithium ion battery material | |
| CN102983326A (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN102916171B (en) | Concentration-gradually-changed spherical lithium nickel manganese oxide cathode material and preparation method thereof | |
| CN103474646B (en) | A kind of mesh structural porous lithium-rich manganese-based anode material for lithium-ion batteries and preparation method thereof | |
| CN103887483A (en) | Doped and modified ternary positive electrode material and preparation method thereof | |
| CN102832387B (en) | Layer-structured ternary material with rich lithium and high manganese as well as preparation method and application thereof | |
| CN105789568A (en) | Sulfur element doped lithium-rich lithium manganese oxide material and preparation method thereof | |
| CN101139108A (en) | Method for preparing layered lithium, nickel, cobalt and manganese oxide anode material for lithium ion battery | |
| CN102723494A (en) | Doped and modified high-temperature lithium manganate cathode material and preparation method thereof | |
| CN104979549A (en) | Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material | |
| CN102875130A (en) | Method for preparing doped lithium-enriched solid solution cathode material by using carbon-added compound | |
| CN114156444A (en) | Sodium-ion battery positive electrode material with symbiotic layered structure and preparation method and application thereof | |
| CN102881875A (en) | Method for preparing lithium-rich solid solution cathode material doped with divalent ions through partial dissolution | |
| CN108735993B (en) | Preparation method of Co and Al Co-doped high-nickel manganese-based oxide cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140521 Termination date: 20151104 |
|
| EXPY | Termination of patent right or utility model |