CN101030639B - Lithium-ion battery positive material and its production - Google Patents
Lithium-ion battery positive material and its production Download PDFInfo
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- CN101030639B CN101030639B CN2006100204413A CN200610020441A CN101030639B CN 101030639 B CN101030639 B CN 101030639B CN 2006100204413 A CN2006100204413 A CN 2006100204413A CN 200610020441 A CN200610020441 A CN 200610020441A CN 101030639 B CN101030639 B CN 101030639B
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- lithium
- limn2o4
- nickel
- base material
- cobalt acid
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 title claims description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 43
- 229910052744 lithium Inorganic materials 0.000 claims description 42
- 229910017052 cobalt Inorganic materials 0.000 claims description 29
- 239000010941 cobalt Substances 0.000 claims description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 238000003801 milling Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 abstract 2
- 229910014981 LiaNixCoyMnzO2 Inorganic materials 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 28
- 238000002474 experimental method Methods 0.000 description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 238000001467 acupuncture Methods 0.000 description 15
- 239000007774 positive electrode material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 241001074085 Scophthalmus aquosus Species 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910013733 LiCo Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910015207 Ni1/3Co1/3Mn1/3O Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910011669 LiNi0.7Co0.2Mn0.1O2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
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Abstract
The present invention is concerned with anode material of Li-ion battery. Add at least one mixed metal oxide to Ni-based composites, and the latter is LiaNixCoyMnzO2, 0.97<=a<=1.07, 0.3<=x <=0.9, 0<=y<=0.5, 0<=z<=0.5. The mixed metal oxide contains LiCoO2, doped compound of LiCoO2 or doped compound of LiMn2O4. This invention also opens the production of the said anode material. The anode material is cheaper and better than LiMn2O4, and the production of anode material is easy for produce and control.
Description
Technical field
The present invention relates to the electrode material of lithium ion battery, be specifically related to a kind of positive electrode and this preparation methods of lithium ion battery.
Background technology
Cobalt acid lithium, lithium nickelate and LiMn2O4 are lithium battery positive electrode active materials commonly used, the commercialization of cobalt acid lithium the earliest, technology is the most ripe, thereby the stability of material is better relatively, the processing behavior is fine, compacted density height (3.6～3.9g/cm3), specific discharge capacity higher relatively (138～142mAh/g), the Stability Analysis of Structures of material, good cycle (capability retentions 88～91% that the 1C circulation is 300 times), the voltage platform of material higher (being 80% more than the 3.6V) and more stable, good with the compatibility of electrolyte, but there is the further development difficulty of energy density big (development space is less) in it, resource scarcity, and price is expensive and fluctuation is bigger, shortcomings such as fail safe, particularly over-charging are relatively poor.Spinel lithium manganate aboundresources, low price, fail safe is good, operating voltage height (platform time height, 3.6V more than be 90%), preparation technology is simple, material is pollution-free, advantages such as good stability, but have low (the theoretical 148mAh/g of capacity, actual 100mAh/g), bad with the compatibility of electrolyte, during deep discharge, the rugged change of lattice takes place in material structure easily, cause capacity attenuation very fast, all the more so when high temperature.The compacted density of material lower (＜3.0g/cm3) wait not enough.(general formula is Li to nickel-base material
aNi
xCo
yMn
zO
2(0.97≤a≤1.07 wherein, 0.3≤x≤0.9,0≤y≤0.5,0≤z≤0.5)) grew up in recent years, price is than the sour lithium of cobalt cheap about 1/3, (the 1C capacity is brought into play about 145～160mAh/g) than cobalt acid lithium height in the specific discharge capacity performance, it is superior that the anti-over-charging performance is bored sour lithium, circulation time capacity and platform conservation rate are than the sour lithium height of cobalt, but it exists output voltage to bore the low about 100mV (being 50% more than the 3.6V) of sour lithium, and compacted density is low than the sour lithium of cobalt, is 3.3～3.6g/cm3, high temperature, capacity during low temperature keeps remaining to improve anti-internal short-circuit (acupuncture) poor-performing.
Summary of the invention
At the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of positive electrode material of lithium secondary cell, and (general formula is Li to this material than nickel-base material
aNi
xCo
yMn
zO
2, 0.97≤a≤1.07,0.3≤x≤0.9,0≤y≤0.5,0≤z≤0.5 wherein) and have higher output voltage and compacted density, have more cheap price and more superior chemical property again than cobalt acid lithium simultaneously.
Another object of the present invention is to provide the preparation method of above-mentioned positive electrode.
For achieving the above object, the present invention has adopted following technical scheme:
The invention discloses a kind of anode material for lithium-ion batteries, be doped with at least a composite metal oxide in nickel-base material, the general formula of described nickel-base material is Li
aNi
xCo
yMn
zO
2, 0.97≤a≤1.07,0.3≤x≤0.9,0≤y≤0.5,0≤z≤0.5 wherein, described composite metal oxide comprises the doped compound of doped compound, LiMn2O4 or the LiMn2O4 of cobalt acid lithium, cobalt acid lithium.
Preferably, described composite metal oxide is cobalt acid lithium or LiMn2O4, and promptly in preferred version, anode material for lithium-ion batteries is nickel-base material doping cobalt acid lithium or LiMn2O4 or their mixture, further preferred nickel-base material doping cobalt acid lithium.
Described cobalt acid lithium or the weight percent content of its doped compound in positive electrode are 0～80%, and described LiMn2O4 or the weight percentage of its doped compound in positive electrode are 0～30%.
Preferably, described cobalt acid lithium or the weight percent content of its doped compound in positive electrode are 20%～60%.
Perhaps preferred, described LiMn2O4 or the weight percent content of its doped compound in positive electrode are 10%～25%.
The invention also discloses the preparation method of above-mentioned anode material for lithium-ion batteries, described method comprises step, with after composite metal oxide mixes, adopts high energy ball mill to carry out mix grinding nickel-base material.
The rotating speed of described ball mill ball milling is 20r/min～300r/min, and the time of described ball milling is 1 hour～24 hours.
Described high energy ball mill is planetary mills, stirs and grind or vibration milling.
Described method further comprises step, and the mixture behind the ball milling was dried by the fire 5～15 hours under 120 ℃～180 ℃ conditions.
In the present invention, term " doped compound " is meant: do not changing under the raw-material intrinsic structure prerequisite, be mixed with a small amount of (trace) other element to improve a class material of a certain performance of material in the part dot matrix of its crystal structure or duct; Such as, in specific embodiments of the invention, the doped compound of cobalt acid lithium selects for use the doping of the Mn element that mixed to bore sour lithium LiCo
0.99Mn
0.01O
2, the doped compound of LiMn2O4 is selected the adulterated lithium manganate LiMn of mixed Ti, Cu and Mg element for use
0.97Ti
0.01Cu
0.01Mg
0.01O
2
Because adopted above scheme, the beneficial effect that the present invention is possessed is:
1, makes full use of the premium properties of LiMn2O4, the sour lithium of brill and nickel-base material, improved the compacted density of composite material by use boring sour lithium, by using nickel-base material to improve specific discharge capacity and cycle performance, the security performance of composite material and having reduced the cost of material, use LiMn2O4 to improve the fail safe of composite material, the platform voltage of raising material and the cost of reduction material, for lithium ion battery provides a kind of very new system positive electrode active materials of high performance-price ratio that has.2, the new material that proposes of the present invention is more cheap than the sour lithium price of cobalt, performance is more superior, and capacity that the specific discharge capacity of material, compacted density, circulation are 300 times and platform conservation rate and output voltage all can reach higher level; All above 130mAh/g, and most ofly surpass 140mAh/g such as, the specific discharge capacity of material, even up to 148mAh/g; Compacted density is all above 3.3g/cm
3, and most of 3.5g/cm that surpasses
3, circulate 300 times capacity and platform conservation rate be all more than 90%, the most of 3.7V that surpasses of output voltage, and 3C/5V and other security performance detect all to be passed through, and the cost of this system material bores sour lithium low 10～15%.3, the new material preparation method that proposes of the present invention simple, be easy to suitability for industrialized production and control.
Description of drawings
Fig. 1 is the positive electrode (a) of the embodiment of the invention 1 and the discharge curve first of nickel-base material of the prior art (b), LiMn2O4 (c) and cobalt acid lithium (d);
Fig. 2 is the positive electrode cycle efficieny curve chart of the embodiment of the invention 1.
Embodiment
Also the present invention is described in further detail in conjunction with the accompanying drawings below by specific embodiment.
Get sour lithium of brill and nickel-base material LiNi at 6: 4 by mass ratio
0.6Co
002Mn
0.2O
2, be medium with the zirconia ball, vibration milling mixed in 2.5 hours, and ball milling speed is 100r/min, takes out in 150 ℃ of baking 10h and gets composite material of the present invention.
With this composite material is positive active material, is negative electrode active material with graphite, makes 063048S box hat battery according to lithium ion battery manufacture craft commonly used in the prior art.Take the battery of stating making and carry out electrochemical property test, a is the discharge curve first of this battery among Fig. 1, and Fig. 2 is the cycle efficieny curve of this battery.The result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 147mAh/g, output voltage average out to 3.75V, and compacted density is 3.70g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 95.3% and 94.9%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Embodiment 2
Get cobalt acid lithium and nickel-base material Li at 5: 95 by mass ratio
0.97Ni
1/3Co
1/3Mn
1/3O
2, be medium with the zirconia ball, vibration milling mixed in 24 hours, and ball milling speed is 20r/m i n.Take out in 150 ℃ of baking 10h and get composite material of the present invention.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 145mAh/g, output voltage 3.71V, compacted density 3.65g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 96.8% and 95.7%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Get sour lithium of brill and nickel-base material Li at 80: 20 by mass ratio
1.03Ni
0.4Co
0.3Mn
0.29O
2, be medium with the zirconia ball, vibration milling mixed in 1 hour, and ball milling speed is 300r/min.Take out in 150 ℃ of baking 10h and get composite material of the present invention.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 141mAh/g, and output voltage is 3.77V, compacted density 3.86g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 92.1% and 92.3%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Get cobalt acid lithium and nickel-base material Li at 20: 80 by mass ratio
0.97Ni
0.90Mn
0.11O
2, be medium with the zirconia ball, vibration milling mixed in 3 hours, and ball milling speed is 100r/min.Take out in 150 ℃ of baking 10h and get composite material of the present invention.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 148mAh/g, output voltage 3.65V, and compacted density is 3.45g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 94.3% and 92.9%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Embodiment 5
Get cobalt acid lithium and nickel-base material LiNi at 50: 50 by mass ratio
0.7Co
0.2Mn
0.1O
2, be medium with the zirconia ball, vibration milling mixed in 4 hours, and ball milling speed is 200r/min.Take out in 150 ℃ of baking 10h and get composite material of the present invention.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 143mAh/g, output voltage 3.73V, compacted density 3.55g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 93.8% and 91.7%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Embodiment 6
Get LiMn2O4 and nickel-base material LiNi at 30: 70 by mass ratio
0.6Co
0.2Mn
0.2O
2, be medium with the zirconia ball, vibration milling mixed in 1 hour, and ball milling speed is 300r/min.Take out in 150 ℃ of baking 10h and get composite material of the present invention.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 136mAh/g, output voltage 3.76V, compacted density 3.3g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 91.5% and 90.7%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Embodiment 7
Get LiMn2O4 and nickel-base material Li at 5: 95 by mass ratio
0.97Ni
1/3Co
1/3Mn
1/3O
2, be medium with the zirconia ball, vibration milling mixed in 3 hours, and ball milling speed is 200r/m i n.Take out in 150 ℃ of baking 10h and get composite material of the present invention.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 146mAh/g, output voltage 3.7V, compacted density 3.56g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 96.7% and 95.8%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Embodiment 8
Get LiMn2O4 and nickel-base material Li at 10: 90 by mass ratio
1.03Ni
0.4Co
0.3Mn
0.29O
2, be medium with the zirconia ball, vibration milling mixed in 2 hours, and ball milling speed is 200r/min.Take out in 150 ℃ of baking 10h and get composite material of the present invention.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 141mAh/g, and output voltage is 3.71V, compacted density 3.50g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 93.7% and 94.1%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Embodiment 9
Get LiMn2O4 and nickel-base material Li at 15: 85 by mass ratio
0.97Ni
0.90Mn
0.11O
2, be medium with the zirconia ball, vibration milling mixed in 2 hours, and ball milling speed is 200r/min.Take out in 150 ℃ of baking 10h and get composite material of the present invention.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 138mAh/g, output voltage 3.74V, compacted density 3.3g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 93.4% and 91.8%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Embodiment 10
Mass ratio is got and is bored sour lithium (the cobalt acid lithium that uses with Comparative Examples is identical), nickel-base material LiNi at 30: 50: 20
0.7Co
0.2Mn
0.1O
2Reach the LiMn2O4 vibration milling and mixed in 2.5 hours, ball milling speed is 200r/min.Take out in 150 ℃ of baking 10h and get composite material of the present invention.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 135mAh/g, output voltage 3.70V, compacted density 3.52g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 91.7% and 90.9%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Embodiment 11
Mass ratio is got doping cobalt acid lithium LiCo at 50: 30: 20
0.99Mn
0.01O
2, nickel-base material LiNi
0.7Co
0.2Mn
0.1O
2And adulterated lithium manganate LiMn
0.97Ti
0.01Cu
0.01Mg
0.01O
2Vibration milling mixed in 2.5 hours, and ball milling speed is 200r/min.Take out in 150 ℃ of baking 10h and get composite material of the present invention.
Prepare battery with embodiment 1 identical method and carry out electrochemical property test, the result shows that the specific discharge capacity of the positive electrode that this embodiment prepares is 134mAh/g, output voltage 3.75V, compacted density 3.61g/cm
3, circulate 300 times capacity and platform conservation rate are respectively 92.7% and 92.9%.
The security performance testing result of battery shows: composite material keeps experiment, acupuncture, heavy impact etc. all can pass through at the capacity that overcharges (3C/5V), external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃.
Comparative Examples 1
With nickel-base material LiNi
1/3Co
1/3Mn
1/3O
2Being positive active material, is negative electrode active material with graphite, makes 063048S box hat battery according to lithium ion battery manufacture craft identical among the embodiment 1.Take the battery of stating making and carry out electrochemical property test, b is the discharge curve first of this battery among Fig. 1, and average output voltage is 3.69V, and behind 300 cycles that circulate, discharge capacitance is 89%, and the compacted density of positive plate is 3.3g/cm
3The security performance testing result of battery is as follows: composite material overcharges (3C/5V) better performances, and the capacity of external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃ keeps experimental result better, and acupuncture performance is relatively poor.
Comparative Examples 2
With identical LiMn2O4 used among the embodiment is positive active material, is negative electrode active material with graphite, makes 063048S box hat battery according to lithium ion battery manufacture craft identical among the embodiment 1.Take the battery of stating making and carry out electrochemical property test, c is the discharge curve first of this battery among Fig. 1, and behind 300 cycles that circulate, discharge capacitance is 82%; The compacted density of positive plate is 2.6g/cm
3The security performance testing result of battery is as follows: composite material overcharges (3C/5V) better performances, the capacity of external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃ keep and the acupuncture experimental result better.
Comparative Examples 3
With cobalt acid lithium used among the embodiment is positive active material, is negative electrode active material with graphite, makes 063048S box hat battery according to present lithium ion battery manufacture craft.Take the battery of stating making and carry out electrochemical property test, d is the discharge curve first of this battery among Fig. 1, and behind 300 cycles that circulate, discharge capacitance is 85%; The security performance testing result of battery is as follows: composite material overcharges (3C/5V) poor-performing, and the capacity of external short circuit, high temperature 130 ℃ of baking ovens experiments, 55 ℃ of high temperature and low temperature-20 ℃ keeps and the acupuncture experimental result can.
By contrast, we are not difficult to find that mixed Ni sill provided by the invention is than pure nickel-base material output voltage height, and capacity brings into play and cycle performance bores sour lithium and LiMn2O4 will be got well, price is cheap than the sour lithium of cobalt, thereby simultaneously owing in material, added the compacted density that cobalt acid lithium has increased material, make it to have better processing behavior, this material has bigger application prospect.
Claims (5)
1. anode material for lithium-ion batteries is characterized in that: be doped with cobalt acid lithium, LiMn2O4 and/or their doped compound in nickel-base material, the general formula of described nickel-base material is Li
aNi
xCo
yMn
zO
2, 0.97≤a≤1.07,0≤y≤0.5 wherein;
And described nickel-base material mix simultaneously cobalt acid lithium and/or the doped compound of cobalt acid lithium and the doped compound of LiMn2O4 and/or LiMn2O4, x=0.7, z=0.1, and described cobalt acid lithium or the weight percent content of its doped compound in positive electrode are 30～50%, and described LiMn2O4 or the weight percentage of its doped compound in positive electrode are 20%.
2. the preparation method of the described anode material for lithium-ion batteries of claim 1, it is characterized in that: described method comprises step, with after composite metal oxide mixes, adopts high energy ball mill to carry out mix grinding nickel-base material.
3. preparation method according to claim 2 is characterized in that: the rotating speed of described high energy ball mill ball milling is 20r/min～300r/min, and the time of described ball milling is 1 hour～24 hours.
4. preparation method according to claim 2 is characterized in that: described high energy ball mill is planetary mills, stirs and grind or vibration milling.
5. according to the arbitrary described preparation method of claim 2～4, it is characterized in that: described method further comprises step, and the mixture behind the ball milling was dried by the fire 5～15 hours under 120 ℃～180 ℃ conditions.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100204413A CN101030639B (en) | 2006-03-02 | 2006-03-02 | Lithium-ion battery positive material and its production |
| HK08100079.6A HK1106070A1 (en) | 2006-03-02 | 2008-01-04 | A kind of anode materials for li-ion battery and its preparation method |
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|---|---|---|---|
| CN2006100204413A CN101030639B (en) | 2006-03-02 | 2006-03-02 | Lithium-ion battery positive material and its production |
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| CN101030639B true CN101030639B (en) | 2011-07-06 |
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|---|---|---|---|---|
| CN101685878B (en) * | 2008-09-27 | 2013-09-18 | 深圳市比克电池有限公司 | Preparation method of polymer lithium ion battery |
| CN101783424A (en) * | 2009-01-15 | 2010-07-21 | 深圳市比克电池有限公司 | Method for pre-charging lithium ion battery |
| WO2010081422A1 (en) * | 2009-01-15 | 2010-07-22 | 深圳市比克电池有限公司 | Pre-charging method for lithium-ion battery |
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| JP6156713B2 (en) | 2012-03-07 | 2017-07-05 | 日産自動車株式会社 | Positive electrode active material, positive electrode for electric device and electric device |
| JP6112380B2 (en) | 2012-03-07 | 2017-04-12 | 日産自動車株式会社 | Positive electrode active material, positive electrode for electric device and electric device |
| KR20150032743A (en) * | 2012-07-20 | 2015-03-27 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | High voltage cathode compositions for lithium-ion batteries |
| JP6035689B2 (en) | 2012-08-02 | 2016-12-07 | 日産自動車株式会社 | Method for producing non-aqueous organic electrolyte secondary battery |
| US11228034B2 (en) * | 2014-12-09 | 2022-01-18 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery and rechargeable lithium battery |
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| CN1345101A (en) * | 2000-09-29 | 2002-04-17 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| CN1682391A (en) * | 2002-09-18 | 2005-10-12 | 株式会社东芝 | Nonaqueous electrolyte secondary cell |
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