CN104347868A - Magnesium-containing lithium-rich layered positive electrode material for lithium ion batteries, and preparation method thereof - Google Patents
Magnesium-containing lithium-rich layered positive electrode material for lithium ion batteries, and preparation method thereof Download PDFInfo
- Publication number
- CN104347868A CN104347868A CN201310334890.5A CN201310334890A CN104347868A CN 104347868 A CN104347868 A CN 104347868A CN 201310334890 A CN201310334890 A CN 201310334890A CN 104347868 A CN104347868 A CN 104347868A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- lithium ion
- lithium
- ion battery
- preparation
- 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.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 15
- 239000011777 magnesium Substances 0.000 title claims description 42
- 229910052749 magnesium Inorganic materials 0.000 title claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 8
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000000227 grinding Methods 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910015118 LiMO Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 11
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 8
- 239000011812 mixed powder Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 5
- 229910013716 LiNi Inorganic materials 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910010085 Li2MnO3-LiMO2 Inorganic materials 0.000 description 1
- 229910010099 Li2MnO3—LiMO2 Inorganic materials 0.000 description 1
- 229910015243 LiMg Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
Abstract
The present invention relates to a positive electrode material for lithium ion batteries, particularly to a Mg-containing lithium-rich layered positive electrode material Li[LixNiaCobMncMgd]O2 and a preparation method thereof, and belongs to the technical field of lithium ion battery positive electrode material preparation. According to the present invention, the chemical formula of the material is Li[LixNiaCobMncMgd]O2, wherein x+a+b+c+d is 1, x is more than 0 and is less than or equal to 0.3, a is more than 0 and is less than or equal to 0.3, b is more than 0 and is less than or equal to 0.3, c is more than 0 and is less than or equal to 0.6, and d is more than 0 and is less than 0.1; the preparation method comprises: pre-grinding dispersing the weighed oxide, the weighed carbonate and other raw materials, carrying out ultra-fine grinding to obtain the slurry with the particle size of less than 300 nm, carrying out spray drying, and carrying out a high temperature calcination solid phase reaction on the spray-dried powder to obtain the final product; and the material has advantages of high tap density, high discharge specific capacity, good rate performance, low raw material cost, low production cost, and simple preparation process.
Description
Technical field
The present invention relates to anode material for lithium ion battery, be specially a kind of containing Mg rich lithium layered cathode material Li [Li
xni
aco
bmn
cmg
d] O
2and preparation method thereof, belong to technical field prepared by anode material for lithium-ion batteries.
Background technology
Along with the application of lithium ion battery is increasingly extensive, people are also improving constantly the requirement of lithium ion battery, and especially electric automobile is in the urgent need to the lithium ion battery of high security, high-energy-density, high power, Large Copacity, long-life, high-environmental, low cost.Commercial Li-ion battery major part uses cobalt acid lithium as positive electrode, but its cost is high, and energy density is limited, is difficult to satisfy the demand, and people are in the urgent need to the material of alternative cobalt acid lithium.Stratiform Li
2mnO
3-LiMO
2solid solution structure material is owing to having higher specific capacity (being greater than 200mAh/g), Heat stability is good, and cycle performance is good, cheap and become the focus of Recent study.But also there is the shortcomings such as irreversible capacity is first higher, high rate performance is bad in this type of material.
Because rich lithium solid solution structure is complicated, present stage is mainly through the coated raising conductivity of oxide.The research that ternary material improves chemical property by doping vario-property has had a lot of year, wherein more with certain element in alternative Ni, Co, Mn threes such as transition metal ions.As Mg
2+ion
with Ni
2+ion
radius is close, mixes the Mg in lattice
2+ion can play supporting construction effect in electrochemical process, thus can improve its overcharging resisting and cycle performance.If the people such as Luo are at Synthesis characterization and thermal stability of LiNi
1/3mn
1/3co
1/3-zmg
zo
2, LiNi
1/3-zmn
1/3co
1/3mg
zo
2and LiNi
1/3-zmn
1/3-zco
1/3mg
zo
2.Chem Mater, has prepared with the coprecipitation of soluble salt the LiMg mixing Mg in 2010,22:1164-1172
xco
1-xo
2and LiNi
1/3mn
1/3co
1/3-z(MnMg)
z/2o
2positive electrode, experiment shows that Mg doping not only improves cycle performance, and the grain diameter increase after roasting improves the thermal stability of material.
Have several patent once to relate to the doping of rich lithium Solid-solution elements, the U57238450 patent as Te Nuo company of the U.S. provides a kind of lithium ion secondary battery anode material, and its chemical formula is: Li [Li
(1-2x)/3m
ymn
(2-x)/3ni
(x-y)] O
2, wherein M is one or more in Ca, Cu, Mg or Zn, 0.15≤x≤0.35,0.02≤y≤0.1.This patent gives the composition containing Mg in an embodiment: Li
1.3mg
0.025mn
0.65ni
0.025o
2, be LiMnO
2the doping of base stratified material, without cobalt, capacity is very low first, only has 176mAh/g, not because having any improvement containing Mg performance.The US7358009 patent in laboratory, U.S. Argonne provides the material that a kind of composition meets following formula: xLiMO
2. (1-x) Li
2m'O
3, M is that to be less than 51 at least two different average valences be the metallic element of 2 to atomic number, M' be Ti, Mn, Zr, Ru and Sn wherein one or more.M is that (further, M selects from Ti, V, Cr, Fe, Mn, Co, Ni, Cu, and further, M is Mn and Ni for the element of transition metal the first row; M can by Li, Mg, Al or Sn Some substitute); And the one-tenth that the US20090220859Al of Samsung (publication number) provides a kind of anode material for lithium-ion batteries in careful patent is grouped into, for: Li [Li
xme
ym
z] O
2+d(x+y+z=1,0 < x < 0.33,0 < z < 0.1,0≤d≤0.1), wherein Me is in following metal: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Mg, Zr, B, and M is one in following metal: Mo, W, Ir, Ni, Mg.These two patents are all only broadly mentioned M and can be substituted by element portions such as Mg, do not provide the related embodiment containing Mg, in depth do not study, the data that non-sampling performance improves.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion battery with containing rich lithium layered cathode material of Mg and preparation method thereof, by the interpolation of magnesium elements, improve material discharge capacity first, improve the rate charge-discharge performance of material, improve the tap density of material.Li [Li of the present invention
xni
aco
bmn
cmg
d] O
2it is high that material has tap density, and specific discharge capacity is high, the good feature of high rate performance, and the cost of raw material and production cost low, preparation technology is simple.
Specifically, for realizing object of the present invention, the present invention relates to two aspects:
On the one hand, the invention provides a kind of lithium ion battery with containing the rich lithium Layered Structural Positive Electrode Materials of Mg, its chemical formula is: Li [Li
xni
aco
bmn
cmg
d] O
2, wherein: x+a+b+c+d=1,0 < x≤0.3,0 < a≤0.3,0 < b≤0.3,0.4 < c≤0.6,0 < d < 0.1.The microstructure of the rich lithium layered cathode material described in this is by Li
2mnO
3and LiMO
2two kinds of components form solid solution, wherein, and M=Ni, Co, Mn, Mg.
The present invention is at Li [Li
xni
aco
bmn
c] O
2add appropriate magnesium in layered composite structure material, one significantly progressive be magnesium add the tap density significantly improving material, improve the high rate performance of material simultaneously.
X, a, b, c, d are x+a+b+c+d=1, and the value of x, a, b, c, d is preferably: x=0.17 ~ 0.2, a=0.13 ~ 0.16, b=0.13 ~ 0.16, c=0.48 ~ 0.55, d=0.002 ~ 0.04.
X, a, b, c, d are x+a+b+c+d=1, and the value of x, a, b, c, d more preferably x=0.17 ~ 0.19, a=0.15, b=0.15, c=0.5 ~ 0.53, d=0.002 ~ 0.04.
X, a, b, c, d are x+a+b+c+d=1, and the value of x, a, b, c, d more preferably x=0.2, a=0.13, b=0.13, c=0.48 ~ 0.54, d=0.002 ~ 0.04 again.
X, a, b, c, d are x+a+b+c+d=1, and the value of x, a, b, c, d is more preferably: x=0.2, a=0.13, b=0.13, c=0.51 ~ 0.54, d=0.005 ~ 0.03.
X, a, b, c, d are x+a+b+c+d=1, and the value of x, a, b, c, d most preferably is: x=0.2, a=0.13, b=0.13, c=0.52 ~ 0.54, d=0.005 ~ 0.02.
On the other hand, the present invention relates to the preparation method of synthesizing lithium ion battery with rich lithium Layered Structural Positive Electrode Materials, be specially:
(1). weighing mol ratio respectively by above-mentioned stoichiometric proportion is: Li: Ni: Co: Mn: Mg=(1+x): the oxide of a kind of and magnesium in the oxide of a kind of, the nickel in the lithium hydroxide of a: b: c: d and lithium carbonate, the oxide of cobalt, the oxide of manganese and manganese carbonate, mixing after weighing;
(2). by the mixture that step (1) obtains, be equipped with deionized water as dispersion liquid, be made into the mixed slurry of solid content 10-30wt%, pre-grinding disperses;
(3). the slurry after step (2) pre-grinding is proceeded to the further Ultrafine Grinding 1 ~ 8h of sand mill, obtain granularity be less than the Ultrafine Grinding of 300nm after slurry;
(4). step (3) gained slurry is carried out spray drying treatment; spray drying condition: inlet temperature 120-220 DEG C; outlet temperature 70-100 DEG C; the slurry of whipping step (3) gained constantly in spray-drying process; to avoid the slurry layering of step (3) gained, obtain spray-dried powders;
(5). the spray-dried powders of step (4) gained is carried out high-temperature roasting solid phase reaction under 850 ~ 1000 DEG C of air atmospheres, and insulation 10 ~ 40h, cools to room temperature with the furnace, obtains Li [Li
xni
aco
bmn
cmg
d] O
2powder product.
Slurry granularity after Ultrafine Grinding described in described step (3) is: D50≤300nm.
Slurry granularity after Ultrafine Grinding described in described step (3) is preferably: D50≤200nm.
Slurry granularity after Ultrafine Grinding described in described step (3) most preferably is: D50≤100nm.
In the preparation process in accordance with the present invention, the particle diameter of material to be made enough little by grinding of step (3), find through experiment, the performance of particle diameter on final products of step (3) gained slurry has appreciable impact, as shown in Figure 1, process through step of the present invention (3) different grinding technology can obtain different grain size slurry, and the granularity of sample is less, and the discharge capacity first finally preparing product is higher.For the purpose of unification, embodiments of the invention all adopt identical grinding technology, ensure that the granularity of sample is basically identical.
Utilize Li of the present invention
1.2co
0.13ni
0.13mn
0.535mg
0.005o
2material (embodiment 2) is in the voltage range of 2 ~ 4.8V, and 0.1C first discharge capacity can reach 265.7mAh/g, improves 6% than the sample of comparative example; Utilize Li of the present invention
1.2co
0.13ni
0.13mn
0.497mg
0.043o
2(embodiment 5) material is in the voltage range of 2 ~ 4.8V, along with the increase of d value (i.e. Mg content), the high rate performance of sample improves, d=0.043 sample, 2C discharge capacity reaches 133.2mAh/g, improves for 31% (as shown in Figure 5) than the sample of comparative example.The tap density of material is: 1.61g/cm
3, improve 144% than the sample of comparative example, as shown in table 1.
Table 1 adds the tap density summary sheet of different Mg amount sample after high-temperature roasting
Accompanying drawing explanation
Fig. 1 adopts preparation method of the present invention preparation, because the different grain size slurry sample selecting different abrasive parameters to obtain in step (3) prepares the discharge curve first of final products.
Fig. 2 is the particle size distribution figure of the embodiment of the present invention 2 sample after Ultrafine Grinding.
Fig. 3 is the stereoscan photograph of the spray-dried rear sample of the embodiment of the present invention 2
Fig. 4 is the stereoscan photograph of the embodiment of the present invention 2 sample after high-temperature roasting.
Fig. 5 is the cyclic curve under the different Mg content sample different multiplying condition of the embodiment of the present invention 1 ~ 5.
Embodiment
The present invention will be further described by the following examples.
Comparative example:
By chemical formula Li
1.2co
0.13ni
0.13mn
0.54o
2in each metallic element mol ratio take the MnCO of gross mass 100 grams
3, NiO, Co
3o
4, Li
2cO
3mixed-powder, adds 400ml deionized water as dispersion liquid, is made into the mixed solution of solid content 20%.Mixed liquor is poured in bar type ball grinder, adds the ZrO that diameter 2-5mm does not wait
2ball 350g, carries out pre-grinding 24h; Afterwards mixture paste is transferred in sand mill and carry out Ultrafine Grinding.Ultrafine Grinding ZrO
2bulb diameter 0.5mm, ball material mass ratio 10: 1, grinds 180min.Slurry after Ultrafine Grinding carries out spraying dry, spray-dired inlet temperature 160 DEG C, and outlet temperature 80 DEG C, obtains spray-dried powders.Take 20g powder and be placed in Muffle furnace roasting: be warming up to 900 DEG C of roasting 12h, cool to room temperature with the furnace, obtain not containing the rich lithium layered cathode material of magnesium.
The tap density of material is: 0.66g/cm
3, in the voltage range of 2 ~ 4.8V, 0.1C first discharge capacity is that 251.2mAh/g, 1C discharge capacity reaches 130.6mAh/g, and 2C discharge capacity reaches 101.4mAh/g.
Embodiment 1:
By chemical formula Li
1.2co
0.13ni
0.13mn
0.537mg
0.003o
2in each metallic element mol ratio take the MnCO of gross mass 100 grams
3, NiO, Co
3o
4, Li
2cO
3, MgO mixed-powder, to grind thereafter, spraying dry and the same comparative example of roasting technique.
As shown in table 1 and Fig. 5, the tap density of material is: 0.73g/cm
3, 0.1C first discharge capacity reaches 258.3mAh/g, and than the sample height 7.1mAh/g of comparative example, 1C discharge capacity reaches 140.7mAh/g, and 2C discharge capacity reaches 107.7mAh/g.
Embodiment 2:
By chemical formula Li
1.2co
0.13ni
0.13mn
0.535mg
0.005o
2in each metallic element mol ratio take the MnCO of gross mass 100 grams
3, NiO, Co
3o
4, Li
2cO
3, MgO mixed-powder, to grind thereafter, spraying dry and the same comparative example of roasting technique.
After Ultrafine Grinding, the particle size distribution figure of sample as shown in Figure 2, and D50 is 0.175 μm; The stereoscan photograph of spray-dried rear sample is as shown in Figure 3, spherical in shape; After high-temperature roasting, the stereoscan photograph of sample as shown in Figure 4, and primary particle size is mostly 0.1 ~ 0.3 μm.As shown in table 1 and Fig. 5, the tap density of material is: 0.76g/cm
3, 0.1C first discharge capacity reaches 265.7mAh/g, and improve 6%, 1C discharge capacity than the sample of comparative example and reach 140.6mAh/g, 2C discharge capacity reaches 111.7mAh/g.
Embodiment 3: by chemical formula Li
1.2co
0.13ni
0.13mn
0.530mg
0.011o
2in each metallic element mol ratio take the MnCO of gross mass 100 grams
3, NiO, Co
3o
4, Li
2cO
3, MgO mixed-powder, to grind thereafter, spraying dry and the same comparative example of roasting technique.
As shown in Figure 5, the tap density of material is: 0.90g/cm
3, 0.1C first discharge capacity reaches 241.4mAh/g, and 1C discharge capacity reaches 143.6mAh/g, and 2C discharge capacity reaches 110.3mAh/g, improves 9% than the sample of comparative example.
Embodiment 4:
By chemical formula Li
1.2co
0.13ni
0.13mn
0.513mg
0.027o
2in each metallic element mol ratio take the MnCO of gross mass 100 grams
3, NiO, Co
3o
4, Li
2cO
3, MgO mixed-powder, to grind thereafter, spraying dry and the same comparative example of roasting technique.
As shown in table 1 and Fig. 5, the tap density of material is: 1.48g/cm
3, than comparative example sample improve 124%, 0.1C first discharge capacity reach 212.5mAh/g, 1C discharge capacity reaches 145.0mAh/g, and 2C discharge capacity reaches 121.4mAh/g, than comparative example sample improve 20%.
Embodiment 5:
By chemical formula Li
1.2co
0.13ni
0.13mn
0.497mg
0.043o
2in each metallic element mol ratio take the MnCO of gross mass 100 grams
3, NiO, Co
3o
4, Li
2cO
3, MgO mixed-powder, to grind thereafter, spraying dry and the same comparative example of roasting technique.
The tap density of material is: 1.61g/cm
3, than comparative example sample improve 144%, 0.1C first discharge capacity reach 205.6mAh/g, 1C discharge capacity reaches 154.3mAh/g, and 2C discharge capacity reaches 133.2mAh/g, than comparative example sample improve 31%.
Fig. 5 is the cyclic curve under the different Mg content sample different multiplying condition of the embodiment of the present invention 1 ~ 5.In Figure 5, d is Mg content (with molar basis): d=0 (comparative example); D=0.003 (embodiment 1); D=0.005 (embodiment 2); D=0.011 (embodiment 3); D=0.027 (embodiment 4); D=0.043 (embodiment 5); As shown in Figure 5, the Mg content of the sample of embodiment 5 is the highest, and it is the highest in 0.1C discharge capacity, 1C discharge capacity or 2C discharge capacity; And minimum than the Mg content of the sample of comparative example, it is minimum in 0.1C discharge capacity, 1C discharge capacity or 2C discharge capacity.
Embodiment 6:
By chemical formula Li
1.4co
0.13ni
0.13mn
0.3mg
0.04o
2in each metallic element mol ratio take the MnCO of gross mass 100 grams
3, NiO, Co
3o
4, Li
2cO
3, MgO mixed-powder, to grind thereafter, spraying dry and the same comparative example of roasting technique.Li too high levels in material, Mn content is too low, and 0.1C first discharge capacity only has 150.3mAh/g.
Embodiment 7:
By chemical formula Li
1.05co
0.13ni
0.13mn
0.65mg
0.04o
2in each metallic element mol ratio take the MnCO of gross mass 100 grams
3, NiO, Co
3o
4, Li
2cO
3, MgO mixed-powder, to grind thereafter, spraying dry and the same comparative example of roasting technique.The Li content of material is too low, Mn too high levels, and 0.1C first discharge capacity only has 141.1mAh/g.
Claims (11)
1. lithium ion battery is with containing the rich lithium Layered Structural Positive Electrode Materials of Mg, it is characterized in that: the chemical formula of this material is: Li [Li
xni
aco
bmn
cmg
d] O
2, wherein: x+a+b+c+d=1,0 < x≤0.3,0 < a≤0.2,0 < b≤0.2,0.4 < c≤0.6,0 < d < 0.1.
2. rich lithium Layered Structural Positive Electrode Materials according to claim 1, is characterized in that: described lithium ion battery is by Li with containing the rich lithium Layered Structural Positive Electrode Materials of Mg
2mnO
3and LiMO
2the solid solution that two kinds of components are formed, wherein, M=Ni, Co, Mn, Mg.
3. according to claim 1 or 2, lithium ion battery, with containing the rich lithium Layered Structural Positive Electrode Materials of Mg, is characterized in that: x+a+b+c+d=1, and x=0.17 ~ 0.2, a=0.13 ~ 0.16, b=0.13 ~ 0.16, c=0.48 ~ 0.55, d=0.002 ~ 0.04.
4. according to claim 1 or 2, lithium ion battery, with containing the rich lithium Layered Structural Positive Electrode Materials of Mg, is characterized in that: x+a+b+c+d=1, and x=0.17 ~ 0.19, a=0.15, b=0.15, c=0.5 ~ 0.53, d=0.002 ~ 0.04.
5. according to claim 1 or 2, lithium ion battery, with containing the rich lithium Layered Structural Positive Electrode Materials of Mg, is characterized in that: x+a+b+c+d=1, and x=0.2, a=0.13, b=0.13, c=0.48 ~ 0.54, d=0.002 ~ 0.04.
6. according to claim 1 or 2, lithium ion battery, with containing the rich lithium Layered Structural Positive Electrode Materials of Mg, is characterized in that: x+a+b+c+d=1, and x=0.2, a=0.13, b=0.13, c=0.51 ~ 0.54, d=0.005 ~ 0.03.
7. according to claim 1 or 2, lithium ion battery, with containing the rich lithium Layered Structural Positive Electrode Materials of Mg, is characterized in that: x+a+b+c+d=1, and x=0.2, a=0.13, b=0.13, c=0.52 ~ 0.54, d=0.005 ~ 0.02.
8. as described in any one of claim 1-7, the preparation method of lithium ion battery containing the rich lithium Layered Structural Positive Electrode Materials of Mg is:
(1). weighing mol ratio respectively by the stoichiometric proportion described in the claims is: Li: Ni: Co: Mn: Mg=(1+x): the oxide of a kind of and magnesium in the oxide of a kind of, the nickel in the lithium hydroxide of a: b: c: d and lithium carbonate, the oxide of cobalt, the oxide of manganese and manganese carbonate, mixing after weighing;
(2). by the mixture that step (1) obtains, be equipped with deionized water as dispersion liquid, be made into the mixed slurry of solid content 10-30wt%, pre-grinding disperses;
(3). the slurry after step (2) pre-grinding is proceeded to the further Ultrafine Grinding 1 ~ 8h of sand mill, obtain the slurry after Ultrafine Grinding;
(4). step (3) gained slurry is carried out spray drying treatment; spray drying condition: inlet temperature 120-220 DEG C; outlet temperature 70-100 DEG C; the slurry of whipping step (3) gained constantly in spray-drying process; to avoid the slurry layering of step (3) gained, obtain spray-dried powders;
(5). the spray-dried powders of step (4) gained is carried out roasting under 850 ~ 1000 DEG C of air atmospheres, and insulation 10 ~ 40h, cools to room temperature with the furnace, obtains Li [Li
xni
aco
bmn
cmg
d] O
2powder.
9. preparation method according to claim 8, the slurry granularity after Ultrafine Grinding described in described step (3) is: D50≤300nm.
10. preparation method according to claim 9, D50≤200nm.
11. preparation methods according to claim 9, D50≤100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310334890.5A CN104347868B (en) | 2013-08-02 | 2013-08-02 | A kind of lithium ion battery positive electrode of lithium-rich containing magnesium and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310334890.5A CN104347868B (en) | 2013-08-02 | 2013-08-02 | A kind of lithium ion battery positive electrode of lithium-rich containing magnesium and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104347868A true CN104347868A (en) | 2015-02-11 |
| CN104347868B CN104347868B (en) | 2017-07-14 |
Family
ID=52503013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310334890.5A Active CN104347868B (en) | 2013-08-02 | 2013-08-02 | A kind of lithium ion battery positive electrode of lithium-rich containing magnesium and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104347868B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106025179A (en) * | 2016-06-30 | 2016-10-12 | 湖南桑顿新能源有限公司 | Method for preparing cathode material lithium nickel cobalt aluminate for lithium ion battery by spray drying |
| CN106410186A (en) * | 2016-11-17 | 2017-02-15 | 天津理工大学 | Preparation method and application of lithium-rich layered oxide cathode material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354741A (en) * | 2011-09-09 | 2012-02-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method of high-capacity layered lithium-rich manganese-based oxide |
| CN102364732A (en) * | 2011-11-28 | 2012-02-29 | 上海中聚佳华电池科技有限公司 | Preparation method of lithium abundant cathode material for lithium ion battery |
| JP2012206929A (en) * | 2011-03-16 | 2012-10-25 | Nippon Chem Ind Co Ltd | Method for producing lithium-nickel-manganese-cobalt composite oxide |
| CN102804459A (en) * | 2010-03-19 | 2012-11-28 | 丰田自动车株式会社 | Lithium secondary battery and cathode active material for said lithium secondary battery |
| CN102903925A (en) * | 2012-10-09 | 2013-01-30 | 江苏科捷锂电池有限公司 | Preparation method of Mg-doped ternary cathode material |
| CN103094550A (en) * | 2011-10-31 | 2013-05-08 | 北京有色金属研究总院 | Preparation method of lithium-rich anode material |
-
2013
- 2013-08-02 CN CN201310334890.5A patent/CN104347868B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102804459A (en) * | 2010-03-19 | 2012-11-28 | 丰田自动车株式会社 | Lithium secondary battery and cathode active material for said lithium secondary battery |
| JP2012206929A (en) * | 2011-03-16 | 2012-10-25 | Nippon Chem Ind Co Ltd | Method for producing lithium-nickel-manganese-cobalt composite oxide |
| CN102354741A (en) * | 2011-09-09 | 2012-02-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method of high-capacity layered lithium-rich manganese-based oxide |
| CN103094550A (en) * | 2011-10-31 | 2013-05-08 | 北京有色金属研究总院 | Preparation method of lithium-rich anode material |
| CN102364732A (en) * | 2011-11-28 | 2012-02-29 | 上海中聚佳华电池科技有限公司 | Preparation method of lithium abundant cathode material for lithium ion battery |
| CN102903925A (en) * | 2012-10-09 | 2013-01-30 | 江苏科捷锂电池有限公司 | Preparation method of Mg-doped ternary cathode material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106025179A (en) * | 2016-06-30 | 2016-10-12 | 湖南桑顿新能源有限公司 | Method for preparing cathode material lithium nickel cobalt aluminate for lithium ion battery by spray drying |
| CN106410186A (en) * | 2016-11-17 | 2017-02-15 | 天津理工大学 | Preparation method and application of lithium-rich layered oxide cathode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104347868B (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6574222B2 (en) | Lithium nickel cobalt manganese composite oxide positive electrode material having a spherical or similar spherical layer structure, manufacturing method, positive electrode, lithium ion battery, energy storage power plant or portable memory equipment, and use | |
| CN103794773B (en) | A kind of method of producing high power capacity 523 type tertiary cathode material | |
| CN103904311B (en) | Lithium-rich manganese-based anode material that a kind of surface is coated compound and preparation method thereof | |
| CN101752555B (en) | Method for preparing lithium ion battery anode material LiFePO4 | |
| CN107403930B (en) | Nickel cobalt lithium aluminate cathode material and its preparation method and application | |
| CN103094550B (en) | Preparation method of lithium-rich anode material | |
| JP6708326B2 (en) | Positive electrode material for sodium secondary batteries | |
| CN102983326B (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN105449169A (en) | Lithium ion battery cathode material, preparation method and lithium ion battery | |
| CN107978751A (en) | A kind of high electrochemical activity tertiary cathode material and preparation method thereof | |
| CN101916843A (en) | Method for preparing lithium battery anode material lithium transition metal composite oxide | |
| CN106299352A (en) | The preparation method of positive pole material of secondary 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 | |
| CN106159244A (en) | Lithium battery cathode material, preparation method thereof and lithium ion battery for power | |
| CN102354741A (en) | Preparation method of high-capacity layered lithium-rich manganese-based oxide | |
| CN102881874B (en) | Method for preparing lithium-rich solid solution cathode material through reduction | |
| CN102916169A (en) | Lithium-rich manganese-based anode material and method for manufacturing same | |
| CN102694167A (en) | Modified lithium manganate positive pole material and preparation method thereof | |
| CN103159264A (en) | Method for preparing positive material NCA of lithium ion cell by virtue of pure solid phase method | |
| CN103311513A (en) | High-performance layered solid-solution lithium-battery positive material and preparation method thereof | |
| CN102623691A (en) | Method for preparing lithium nickel manganese oxide serving as cathode material of lithium battery | |
| CN102263238A (en) | Lithium nickel cobalt manganese oxide and preparation method thereof | |
| Jiang et al. | Syntheses of spherical LiMn2O4 with Mn3O4 and its electrochemistry performance | |
| CN105789607A (en) | Preparation method of lithium titanate anode material doped with rare earth | |
| CN101986445A (en) | Method for producing lithium battery cathode material lithium titanate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160322 Address after: 101407 Beijing Yanqi Yanqi Economic Development Zone Huairou District Road No. 3 Applicant after: CHINA AUTOMOTIVE BATTERY RESEARCH INSTITUTE Co.,Ltd. Address before: 100088 Beijing city Xicheng District Xinjiekou Avenue No. 2 Applicant before: General Research Institute for Nonferrous Metals |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240108 Address after: Office 202 of the Foreign Cooperation Bureau of the High tech Zone, No.1 Photovoltaic Road, High tech Zone, Xinyu City, Jiangxi Province, 338004 Patentee after: Youyan New Energy Materials (Jiangxi) Co.,Ltd. Address before: 101407 No.3, Yanqi Road, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: CHINA AUTOMOTIVE BATTERY RESEARCH INSTITUTE Co.,Ltd. |
|
| TR01 | Transfer of patent right |