CN101139108B - Method for preparing layered lithium, nickel, cobalt and manganese oxide anode material for lithium ion battery - Google Patents
Method for preparing layered lithium, nickel, cobalt and manganese oxide anode material for lithium ion battery Download PDFInfo
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- CN101139108B CN101139108B CN2006101130099A CN200610113009A CN101139108B CN 101139108 B CN101139108 B CN 101139108B CN 2006101130099 A CN2006101130099 A CN 2006101130099A CN 200610113009 A CN200610113009 A CN 200610113009A CN 101139108 B CN101139108 B CN 101139108B
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Abstract
The present invention relates to a method to prepare cathode material of layered lithium-nickel-cobalt-manganese oxide applied to lithium ion battery. The corresponding materials of metal manganese powers, compounds of lithium, metal cobalt or compounds of cobalt and compounds of nickel are weighted according to the molar ratio expressed and required in the chemical formula Li<SUB>y</SUB>Ni<SUB>x</SUB>Co<SUB>1-2x</SUB>Mn<SUB>x</SUB>O<SUB>2</SUB>. In the formula, x is more than zero but less than 0.5 and y is more than or equal to 0.9 but less than 1.1; a solvent is added in the materials for wetmilling; and to be dried after wetmilling; then the materials is sintered under high temperature and then to be grinded to acquire the cathode material of layered lithium-nickel-cobalt-manganese oxide. The present invention has the advantages that a wetmilling mixing method is adopted which improves the mixing effect of the materials; a solid phase method is adopted to compound which has the advantages of simple technics process and low cost and is suitable for Industrialized mass production and avoids the complex flows of the body of a wet method before preparation; the metal manganese powers are adopted to replace the traditional manganese compound as materials which greatly improves the tap density of products and can realize higher volume capacity.
Description
Technical field
The present invention relates to the preparation method of the laminated Li-Ni cobalt and manganese oxide anode material that a kind of lithium ion battery uses, belong to the technical field of anode material for lithium-ion batteries preparation.
Background technology
Since Sony in 1992 develops the commercialization lithium ion battery, distinguishing features such as lithium ion battery is big, in light weight with its specific energy, memory-less effect, develop rapidly, being used widely in fields such as mobile phone, portable electronics, military equipment power supply, grapefruit satellite power supplys, also is the first-selected supporting power supply of electric bicycle and electric automobile simultaneously.Anode material for lithium-ion batteries mainly is a cobalt acid lithium in the market, and it has better electrochemical performance, but problem such as its capacity is on the low side, fail safe is not good enough, cost an arm and a leg reveals gradually along with the development of battery, presses for other material and replaces.The material that can substitute cobalt acid lithium at present has lithium nickelate, LiMn2O4, layered lithium manganate etc., and the lithium nickelate capacity is higher, but preparation is difficult, is difficult to the material of synthetic better performances, poor stability; The LiMn2O4 fail safe is good, and cost is low, but its specific capacity is relatively low, and problems such as high temperature circulation less stable have also limited its large-scale application; Layered lithium manganate specific capacity height, but structural instability has limited its development in charge and discharge process.And laminated Li-Ni cobalt and manganese oxide Li
yNi
xCo
1-2xMn
xO
2(0＜x＜0.5,0.9≤y＜1.1) material has than higher capacity and the security performance of cobalt acid lithium, has become to have most at present one of new type lithium ion battery positive electrode of development prospect.
Laminated Li-Ni cobalt and manganese oxide material synthesis method adopts liquid-phase coprecipitation and high temperature solid-state method basically at present, liquid-phase coprecipitation generally is that the aqueous solution of nickel salt, cobalt salt, manganese salt is generated mixed presoma hydroxide or carbonate with lithium hydroxide, NaOH or sodium carbonate co-precipitation, then with the mixture grinding of this hydroxide or carbonate and the compound that contains lithium after high temperature solid-phase sintering obtains end product.As people such as S.Jouanneau (S.Jouanneau, K.W.Eberman, L.J.Krause, and J.R.Dahn.Synthesis, Characteriszation, andElectrochemical Behauior of Improved Li[Ni
xCo
1-2xMn
x] O
2.Joumal of TheElectrochemical Society, 150 (12), 2003:A1637-A1642) with CoSO
4.7H
2O, NiSO
4.6H
2O, MnSO
4.H
2O is a raw material, adopts solution chemical processes LiOH co-precipitation, obtains M (OH) 2 (M=Ni, Co, Mn), and 120 ℃ of oven dry obtain presoma and LiOH.H2O mixing, 900-1100 ℃ of down synthetic Li[Ni
xCo
1-2xMn
x] O
2Ho-Sun Shin (Ho-SunShin, Sang-Ho Park, Chong Seung Yoon, and Yang-Kook Sun.Effect ofFluorine on Electrochemical Properties of LayeredLi[Ni
0.43Co
0.22Mn
0.35] O
2CaheodeMaterials via a Carbonaterocess.Electrochemical and Solid-State Letters, 8 (11), 2005:A559-A563) with NiSO
4, CoSO
4, MnSO
4For raw material sodium carbonate co-precipitation, obtain Ni
0.43Co
0.22Mn
0.35) CO
3, 500 ℃ of following heat treatments obtain oxide, mix 900 ℃ of following 20 hours synthetic products with lithium salts then.The advantage of solution coprecipitation is that each composition of raw material mixes, and can realize higher specific capacity, (is generally less than 2.0g/cm but generally tap density is lower
3), and the presoma preparation is generally cumbersome, complex process, and multicomponent mixture is not easy by metering than precipitation.High temperature solid-state method generally is that the compound with nickel, cobalt, manganese and lithium evenly mixes, direct sintering synthetic product under the high temperature, and this method flow is fairly simple, easy realization of industrialization.As people (Zhaoxiang Wang, YuchengSun, etal.Electrochemical characterization of positive electrode materialLiNi such as Zhaoxiang Wang
1/3Co
1/3Mn
1/3O
2And compatibility with electrolyte for lithium-ionbatteries.Journal of Electrochemical Society, 151 (6), 2004:A914-A921) use Ni
2O
3, Co
2O
3, MnO
2To a certain degree excessive LiOH.H
2O mixes back sintering 24 hours in 850 ℃ of-1100 ℃ of temperature ranges, obtains the LiNi of intact layer structure
1/3Co
1/3Mn
1/3O
2People (Jung-Min Kim, Hoon-TaekChung.The first cycle characteristics of Li[Ni such as Jung-Min Kim
1/3Co
1/3Mn
1/3] O
2Charged upto4.7V.Electrochinica Acta, 49 (2004): 937-944) adopt LiOH.H
2O, Ni (OH)
2, CoNO
3.6H
2O, Mn
3O
4Be raw material, with dry after the ethanol mixing and ball milling, dried powder obtained end product in 12 hours 950 ℃ of insulations.It is raw material that people such as Liao Qinlin (national inventing patent CN1610153A) adopt oxide, hydroxide or the carbonate of nickel, lithium, cobalt, add Ti, Mg, Cr, Mn a kind of element wherein again, in ball mill, mix, at 600 ℃ of-800 ℃ of following pre-burning 5-15 hours, synthesized 5-20 hour down at 700 ℃-900 ℃ then, after pulverizing, ball milling, the classification, obtain end product.Yet the defective that general high temperature solid-state method exists is to cause multiple raw material to mix uneven problem easily, in order to improve mixed effect, the method of general normal employing is to add ethanol equal solvent ball milling to mix, yet the result that adding solvent ball milling mixes usually causes the product tap density on the low side.
Summary of the invention
At the deficiency of above-mentioned technology, the purpose of this invention is to provide a kind of positive electrode Li that lithium ion battery is used for preparing
yNi
xCo
1-2xMn
xO
2The method of (0＜x＜0.5,0.9≤y＜1.1), this method can make the product tap density improve a lot, thereby can improve the matter-loading amount of electrode greatly, improve the battery volume capacity.The Li that this method is synthetic
yNi
xCo
1-2xMn
xO
2(0＜x＜0.5,0.9≤y＜1.1) material has intact α-NaFeO
2Layer structure, specific capacity are greater than 150mAh/g, and tap density is greater than 2.3g/cm
3, being higher than conventional solid-state method is the tap density of raw material synthetic material with the manganese compound.
To achieve these goals, the present invention adopts following technical scheme:
The preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that a kind of lithium ion battery is used presses chemical formula Li with the compound of compound, metallic cobalt or the cobalt of manganese powder, lithium, the compound of nickel
yNi
xCo
1-2xMn
xO
2Express the mole proportioning that requires and take by weighing corresponding above-mentioned raw materials, in the formula, 0＜x＜0.5,0.9≤y＜1.1; In raw material, add solvent and carry out wet-milling; Dry after the wet-milling; Sintering under high temperature grinds and obtains the laminated Li-Ni cobalt and manganese oxide anode material again.
It is the bigger raising that raw material has been realized the product tap density that this method has adopted manganese powder to replace traditional manganese compound, thereby can improve the matter-loading amount of electrode greatly, improves the battery volume capacity.The Li that this method is synthetic
yNi
xCo
1-2xMn
xO
2(0＜x＜0.5,0.9≤y＜1.1) material has intact α-NaFeO
2Layer structure, specific capacity are greater than 150mAh/g, and tap density is greater than 2.3g/cm
3, even can reach 2.7g/cm
3, be the tap density of raw material synthetic material with the manganese compound apparently higher than conventional solid-state method.
In prior art, the mixing of raw material has two kinds basically: a kind of mixed for doing; Another kind of is wet mixing.The present invention has adopted wet-mix method, promptly adopts the method for solubilizer wet-milling to improve raw-material mixed effect.But the method for also not getting rid of dry blend wet mixing combination.
In the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery of the present invention is used, the compound of described lithium is lithium hydroxide or lithium carbonate.Be preferably lithium hydroxide.
In the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery of the present invention is used, the compound of described cobalt is any one in cobalt oxide, cobalt sesquioxide, cobalt protoxide, cobalt oxalate, cobalt acetate, hydroxyl cobalt, cobalt hydroxide, cobalt carbonate and the basic cobaltous carbonate.Be preferably cobalt oxide, cobalt sesquioxide or cobalt protoxide.
In the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery of the present invention is used, the compound of described nickel is any one in nickel sesquioxide, nickel oxide, nickel hydroxide, nickelous carbonate, basic nickel carbonate, nickel oxalate and the nickel acetate.Be preferably nickel sesquioxide or nickel oxide.
In the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery of the present invention is used, in described wet-milling process, the equipment of the wet-milling of being adopted is the general milling machine, rotating speed is 50～70 rev/mins, its wet-milling mode is to add agate ball to carry out wet-milling in raw material and solvent, ball material weight ratio is 0.5-5,0.5-5 hour wet-milling time.
In described wet-milling process, used solvent is water, absolute ethyl alcohol, acetone or ethanol water.The consumption of solvent is unqualified, can reach the consumption that raw material can soak the solvent in the solvent and get final product.The temperature and time of the oven dry after the wet-milling is decided according to employed solvent, is generally 80 ℃～120 ℃, and the time is 10～30 minutes.
In the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery of the present invention is used, described under high temperature in the sintering process, sintering temperature is 900 ℃-1150 ℃, and temperature retention time is 10-40 hour.
Advantage of the present invention is: this method has adopted manganese powder to replace the conventional high-temperature solid phase method to use manganese compound to realize increasing substantially of tap density, can realize higher volume capacity.Method by the solubilizer wet-milling has realized the uniform mixed effect of multiple raw material.The employing solid phase method is synthetic, and technical process is simple, and cost is low, is easy to big industrial production, has avoided wet method to prepare the flow process of precursor complexity.
Further specify the bright method of we by the following examples.
Description of drawings
Fig. 1 is the XRD figure of the synthetic lithium nickel cobalt manganese oxidation thing of the inventive method, and wherein, Fig. 1 a is the XRD figure by the lithium nickel cobalt manganese oxidation thing of embodiment 1 preparation; Fig. 1 b is the XRD figure by the lithium nickel cobalt manganese oxidation thing of embodiment 2 preparations; Fig. 1 c is the XRD figure by the lithium nickel cobalt manganese oxidation thing of embodiment 3 preparations.
Fig. 2 is the charging and discharging curve of the synthetic lithium nickel cobalt manganese oxidation thing of the inventive method (embodiment 1), charging/discharging voltage scope 2.5-4.6V, and current density is 0.2C, and abscissa is a specific capacity, and ordinate is a voltage.
Fig. 3 is the cyclic curve of the synthetic lithium nickel cobalt manganese oxidation thing of the inventive method (embodiment 3), and abscissa is a cycle-index, and ordinate is specific capacity (mAh/g).
Embodiment
The following embodiment 1-12 and the rotating speed of comparative example 1 employed ball mill are 60 rev/mins.The positive electrode stratiform lithium nickel cobalt manganese oxygen thing that following embodiment 1-12 and the prepared lithium ion battery of comparative example 1-2 are used, its chemical formula is: Li
yNi
xCo
1-2xMn
xO
2, in the formula, x=0.125; Y=1.
Embodiment 1:
Take by weighing LiOH.H respectively
2O22.53 gram, Co
3O
420.07 gram, NiO9.43 gram and manganese powder 6.94 grams are put into ball mill, add 100 milliliters of soaked in absolute ethyl alcohol, add 50 gram agate balls, wet-milling 2 hours is taken out, filter, in the corundum crucible of packing into after the oven dry, put into high temperature furnace and carry out sintering, be warmed up to 1000 ℃ by 3 ℃ of/minute intensification speed, be incubated 15 hours, lower the temperature with 0.6 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.XRD figure by the lithium nickel cobalt manganese oxidation thing of embodiment 1 method preparation is Fig. 1 a.First charge-discharge curve by the synthetic lithium nickel cobalt manganese oxidation thing of embodiment 1 method is seen Fig. 2, and in the charging and discharging curve in Fig. 2, abscissa is a specific capacity, and ordinate is a voltage.The charging/discharging voltage scope 2.5-4.6V of lithium nickel cobalt manganese oxidation thing, current density is 0.2C, and abscissa is a specific capacity, and ordinate is a voltage.As shown in Figure 2, be the first charge-discharge curve of embodiment 1 method synthetic material, demonstrate the lithium nickel cobalt manganese oxidation thing that synthesizes with method of the present invention and have capacity characteristic preferably.
Embodiment 2:
Take by weighing LiOH.H respectively
2O22.53 gram, metal Co powder 14.8 grams, Ni
2O
310.19 gram and manganese powder 6.94 grams are put into ball mill, add 100 milliliters of soaked in absolute ethyl alcohol, add 60 gram agate balls, wet-milling 3 hours is taken out, filter, in the corundum crucible of packing into after the oven dry, put into high temperature furnace and carry out sintering, be warmed up to 1150 ℃ by 10 ℃ of/minute intensification speed, be incubated 20 hours, lower the temperature with 2 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.XRD figure by the lithium nickel cobalt manganese oxidation thing of embodiment 2 preparation is Fig. 1 b.
Embodiment 3:
Take by weighing LiOH.H respectively
2O22.53 gram, Co
3O
420.07 gram, Ni
2O
310.19 gram and manganese powder 6.94 grams are put into ball mill, the mixture that adds 100 milliliters of absolute ethyl alcohols and water soaks, add 40 gram agate balls, wet-milling 5 hours is taken out, filter, in the dress corundum crucible of oven dry back, put into sintering furnace, be warmed up to 950 ℃ by 4 ℃ of/minute intensification speed, be incubated 25 hours, lower the temperature with 0.6 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.XRD figure by the lithium nickel cobalt manganese oxidation thing of embodiment 3 preparation is Fig. 1 c.Cyclic curve by the synthetic lithium nickel cobalt manganese oxidation thing of embodiment 3 is seen Fig. 3, and in the cyclic curve of the lithium nickel cobalt manganese oxidation thing of Fig. 3, abscissa is a cycle-index, and ordinate is specific capacity (mAh/g).
Take by weighing Li respectively
2CO
318.48 gram, Co
2O
320.7 gram, NiCO
314.99 gram and manganese powder 6.94 grams are put into ball mill, add 150 milliliters of aqueous solution soaking, add 80 gram agate ball wet-millings 1 hour, take out, filter, pack into after the oven dry in the corundum crucible, put into high temperature furnace and carry out sintering, be warmed up to 1100 ℃ by 3 ℃ of/minute intensification speed, be incubated 15 hours, with the cooling of 2 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.
Take by weighing LiOHH respectively
2O22.53 gram, CoO18.92 gram, NiCO
32Ni (OH)
24H
2O15.8 gram and manganese powder 6.94 grams are put into ball mill, add 150 milliliters of soaked in absolute ethyl alcohol, add 200 gram agate balls, wet-milling 1 hour is taken out, filter, in the corundum crucible of packing into after the oven dry, put into high temperature furnace and carry out sintering, be warmed up to 1000 ℃ by 3 ℃ of/minute intensification speed, be incubated 15 hours, lower the temperature with 0.5 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.
Take by weighing LiOHH respectively
2O22.53 gram, CoC
2O
42H
2O46.19 gram, NiC
2O
42H
2O23.07 gram and manganese powder 6.94 grams are put into ball mill, add 200 milliliters of soaked in absolute ethyl alcohol, add 200 gram agate balls, wet-milling 2 hours is taken out, filter, in the corundum crucible of packing into after the oven dry, put into high temperature furnace and carry out sintering, be warmed up to 1000 ℃ by 3 ℃ of/minute intensification speed, be incubated 24 hours, lower the temperature with 1 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.
Take by weighing LiOHH respectively
2O22.53 gram, Co (CH
3COO)
24H
2062.2 gram, Ni (CH
3COO)
24H
2O31.40 gram and manganese powder 6.94 grams are put into ball mill, add 250 milliliters of acetone and soak, add 400 gram agate balls, wet-milling 0.5 hour is taken out, filter, in the corundum crucible of packing into after the oven dry, put into high temperature furnace and carry out sintering, be warmed up to 900 ℃ by 10 ℃ of/minute intensification speed, be incubated 35 hours, lower the temperature with 2 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.
Take by weighing LiOHH respectively
2O22.53 gram, Co
3O
420.07 gram, Ni (OH)
2H
2O14.00 gram and manganese powder 6.94 grams are put into ball mill, add 150 milliliters of soaked in absolute ethyl alcohol, add 40 gram agate balls, wet-milling 4 hours is taken out, filter, in the corundum crucible of packing into after the oven dry, put into high temperature furnace and carry out sintering, be warmed up to 1000 ℃ by 5 ℃ of/minute intensification speed, be incubated 25 hours, lower the temperature with 1.5 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.
Take by weighing Li respectively
2CO
318.48 gram, Co (OH)
223.47 gram, Ni (OH)
2H
2O14.00 gram and manganese powder 6.94 grams are put into ball mill, add 150 milliliters of acetone and soak, add 320 gram agate balls, wet-milling 1 hour is taken out, filter, in the corundum crucible of packing into after the oven dry, put into high temperature furnace and carry out sintering, be warmed up to 1100 ℃ by 0.5 ℃ of/minute intensification speed, be incubated 10 hours, lower the temperature with 1 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.
Take by weighing LiOHH respectively
2O22.53 gram, hydroxyl cobalt 23.08 grams, Ni (OH)
2H
2O14.00 gram and manganese powder 6.94 grams are put into ball mill, add 150 milliliters of soaked in absolute ethyl alcohol, add 65 gram agate balls, wet-milling 5 hours is taken out, 120 ℃ of oven dry add the polyvinyl alcohol water solution granulation, and addition is polyvinyl alcohol 1 gram, pack into after 120 ℃ of oven dry in the corundum crucible, put into high temperature furnace and carry out sintering, be warmed up to 950 ℃ by 1 ℃ of/minute intensification speed, be incubated 30 hours,, take out with the cooling of 0.4 ℃/component velocity, grind, cross 300 mesh sieves, obtain end product.
Embodiment 11
Take by weighing LiOHH respectively
2O22.53 gram, CoCO
329.86 gram, Ni (OH)
2H
2O14.00 gram and manganese powder 6.94 grams are put into ball mill, add 200 milliliters of soaked in absolute ethyl alcohol, add 100 gram agate balls, wet-milling 1 hour is taken out, filter, in the corundum crucible of packing into after the oven dry, put into high temperature furnace and carry out sintering, be warmed up to 900 ℃ by 5 ℃ of/minute intensification speed, be incubated 40 hours, lower the temperature with 1 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.
Embodiment 12
Take by weighing LiOHH respectively
2O22.53 gram, 2CoCO
3.3Co (OH)
2.H
2O26.73 gram, Ni (OH)
2H
2O14.00 gram and manganese powder 6.94 grams are put into ball mill, add 150 milliliters of soaked in absolute ethyl alcohol, add 50 gram agate balls, wet-milling 3 hours is taken out, filter, in the corundum crucible of packing into after the oven dry, put into high temperature furnace and carry out sintering, be warmed up to 1050 ℃ by 5/ fen intensification speed, be incubated 30 hours, lower the temperature with 1 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.
Comparative Examples 1:
Take by weighing LiOH.H respectively
2O22.53 gram, Co
3O
420.07 gram, NiO9.43 gram and manganese dioxide 11.15 grams are put into ball mill, add the mixture of 100 milliliters of absolute ethyl alcohols and water, add 60 gram agate balls, wet-milling 2 hours is taken out, put into corundum crucible after 120 ℃ of oven dry, put into high temperature furnace and carry out sintering, be warmed up to 1000 ℃ by 4 ℃ of/minute intensification speed, be incubated 10 hours, with the cooling of 0.6 ℃/component velocity, take out, grind, cross 300 mesh sieves, obtain end product.
Comparative Examples 2:
Take by weighing Mn (NO respectively
3)
2.6H
2O25.14g, Ni (NO
3)
2.6H
2O25.5g, Co (NO
3)
2.6H
2O50.5g puts into beaker, adds deionized water, 60 ℃ of following stirring and dissolving, drips 1molLiOH solution, to pH value 12, filter, obtain dark green precipitation, washed several times with water, to pH value is 7,200 ℃ of oven dry 1 day, obtains the black presoma, allocates monohydrate lithium hydroxide 15.67 grams into, mixed 4 hours, in the corundum crucible of packing into, put into sintering furnace, be warmed up to 900 ℃ by 4 ℃ of/minute intensification speed, be incubated 15 hours,, take out with the cooling of 0.6 ℃/component velocity, grind, cross 300 mesh sieves, obtain end product.
In the present invention, as shown in Figure 1, Fig. 1 ( embodiment 1,2,3 XRD figure spectrum, and the collection of illustrative plates of other embodiment 3-12 is similar, slightly) demonstrates with the synthetic lithium nickel cobalt manganese oxidation thing of method of the present invention to have α-NaFeO
2Structure, diffraction maximum is sharp-pointed, shows to have intact crystal formation, and 006/102,108/110 swarming is clear, demonstrates layer structure preferably.Fig. 2 is the first charge-discharge curve of the inventive method synthetic material, demonstrates with the synthetic lithium nickel cobalt manganese oxidation thing of method of the present invention to have capacity characteristic preferably.
In the present invention, in order to detect physics and the chemical property of lithium ion battery of the present invention, carry out structured testing with Dutch X ' Pert PRO MPD type XRD diffractometer with lithium nickel cobalt manganese oxidation thing material; The method of all knowing with the those of ordinary skill under this area, it is assembled into flat test cell carries out electrochemical property test, with lithium ion battery of the present invention lithium nickel cobalt manganese oxidation thing positive electrode 85-92% (percetage by weight), binding agent PVDF (Kynoar) 8-15%, mix the furnishing pulpous state, be coated on the two sides of aluminium foil,, make electrode at air drying.Electrode is formed test cell for the lithium sheet metal.Electrolyte is 1M (mol/L) LiPF
6/ EC+DMC etc., EC are ethylene carbonate, and DMC is a dimethyl carbonate.Charging and discharging currents density 0.2C, discharging and recharging upper and lower limit voltage is 2.5-4.6V, specific capacity computational methods C=mA * h/g, wherein C: specific capacity, temperature is 25 ± 2 ℃, the constant current tester that computerizeds control carries out electrochemistry capacitance and loop test.Charging and discharging curve by the synthetic lithium nickel cobalt manganese oxidation thing of embodiment 1 method is seen Fig. 2; Cyclic curve by the synthetic lithium nickel cobalt manganese oxidation thing of embodiment 3 is seen Fig. 3.
Table 1 is the tap density of synthetic lithium nickel cobalt manganese oxidation thing of the inventive method and contrast sample.The result of table 1 demonstrates with the synthetic lithium nickel cobalt manganese oxidation thing material of method of the present invention (embodiment 1-12) all has higher tap density than solution coprecipitation (comparative example 2) and the synthetic same material (comparative example 1) of general high temperature solid-state method.
The lithium nickel cobalt manganese oxidation thing tap density contrast that table 1 method of the present invention is synthetic
| Tap density/g/cm 3 | |
| Embodiment 1 | 2.53 |
| |
2.69 |
| |
2.43 |
| |
2.75 |
| |
2.55 |
| |
2.65 |
| |
2.32 |
| |
2.61 |
| |
2.72 |
| |
2.45 |
| Embodiment 11 | 2.39 |
| Embodiment 12 | 2.72 |
| Comparative Examples 1 | 2.2 |
| Comparative Examples 2 | 1.9 |
Claims (10)
1. the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing used of a lithium ion battery is characterized in that, the compound of compound, metallic cobalt or the cobalt of manganese powder, lithium, the compound of nickel are pressed chemical formula Li
yNi
xCo
1-2xMn
xO
2Express the mole proportioning that requires and take by weighing corresponding above-mentioned raw materials, in the formula, 0＜x＜0.5,0.9≤y＜1.1; In raw material, add solvent and carry out wet-milling; Dry after the wet-milling; Sintering under high temperature grinds and obtains the laminated Li-Ni cobalt and manganese oxide anode material again.
2. the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery according to claim 1 is used is characterized in that the compound of described lithium is lithium hydroxide or lithium carbonate.
3. the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery according to claim 2 is used is characterized in that the compound of described lithium is a lithium hydroxide.
4. the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery according to claim 1 is used is characterized in that the compound of described cobalt is Co
3O
4, in cobalt sesquioxide, cobalt protoxide, cobalt oxalate, cobalt acetate, cobalt hydroxide, cobalt carbonate and the basic cobaltous carbonate any one.
5. the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery according to claim 4 is used is characterized in that the compound of described cobalt is Co
3O
4, cobalt sesquioxide or cobalt protoxide.
6. the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery according to claim 1 is used, it is characterized in that the compound of described nickel is any one in nickel sesquioxide, NiO, nickel hydroxide, nickelous carbonate, basic nickel carbonate, nickel oxalate and the nickel acetate.
7. the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery according to claim 6 is used is characterized in that the compound of described nickel is nickel sesquioxide or NiO.
8. the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery according to claim 1 is used, it is characterized in that, in described wet-milling process, the equipment of the wet-milling of being adopted is the general milling machine, rotating speed is 50～70 rev/mins, its wet-milling mode is to add agate ball to carry out wet-milling in raw material and solvent, and ball material weight ratio is 0.5-5,0.5-5 hour wet-milling time.
9. the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing that lithium ion battery according to claim 1 is used is characterized in that in described wet-milling process, used solvent is water, absolute ethyl alcohol, acetone or ethanol water.
10. the preparation method of the positive electrode stratiform lithium nickel cobalt manganese oxygen thing of using according to the lithium ion battery of claim 1 is characterized in that, described under high temperature in the sintering process, sintering temperature is 900 ℃-1150 ℃, and temperature retention time is 10-40 hour.
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| CN102664253A (en) * | 2012-05-09 | 2012-09-12 | 奇瑞汽车股份有限公司 | Lithium-rich material and preparation method thereof and lithium ion battery containing same |
| CN103066274B (en) * | 2013-01-23 | 2015-02-25 | 上海电力学院 | Lithium-rich multi-component lithium ion battery positive pole material and preparation method thereof |
| CN103972495B (en) * | 2014-05-16 | 2016-03-23 | 盐城市新能源化学储能与动力电源研究中心 | A kind of preparation method of lithium ion battery anode material nickel LiMn2O4 |
| CN104300145B (en) * | 2014-10-10 | 2017-02-15 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for high-tapping-density modified nickel-cobalt lithium manganate positive material |
| CN104979549A (en) * | 2015-07-29 | 2015-10-14 | 杭州朗鑫新材料科技有限公司 | 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 |
| CN105322157A (en) * | 2015-10-31 | 2016-02-10 | 芜湖迈特电子科技有限公司 | Preparation method of manganese-doped lithium cobalt oxide of lithium polymer battery for charge pal |
| CN105390692A (en) * | 2015-10-31 | 2016-03-09 | 芜湖迈特电子科技有限公司 | Preparation method of lithium manganate compound for lithium polymer battery |
| CN107221667A (en) * | 2017-07-10 | 2017-09-29 | 苏州柏晟纳米材料科技有限公司 | A kind of preparation method of composite metal oxide electrode material |
| CN108448109B (en) * | 2018-03-23 | 2021-07-02 | 中南大学 | Layered lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN108717976B (en) * | 2018-05-24 | 2020-10-23 | 广东邦普循环科技有限公司 | Preparation method of high-density power type nickel cobalt lithium manganate positive electrode material |
| MX2022011873A (en) | 2020-03-27 | 2022-12-13 | Univ Texas | Low-cobalt and cobalt-free, high-energy cathode materials for lithium batteries. |
| CN114300674B (en) * | 2021-12-22 | 2023-11-21 | 广州大学 | LiNi 0.8 Co 0.1 Mn 0.1 O 2 Surface modification method of ternary positive electrode material |
| CN116936778A (en) * | 2023-09-15 | 2023-10-24 | 山东海化集团有限公司 | Sodium ion battery positive electrode material and preparation method thereof |
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