CN101117234B - Method for preparing doping lithium-enriching spinelle lithium manganese oxide - Google Patents
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Abstract
The invention relates to a preparation method for doped lithium-rich spinel-type lithium manganese oxide. The process of the method is as follows: the lithium compound, the manganese compound and the doped metal compound are uniformly mixed, and then calcined in the baking furnace, wherein, the calcination consists of the primary calcination and the secondary calcination, the primary calcination comprises the manganese compound, the doped metal compound and a part of the lithium compound are uniformly mixed and calcined, and then the primary calcination product is obtained; the secondary calcination comprises the primary calcination product and the other part of the lithium compound are mixed and calcined. The material is charged and discharged between 3.0V to 4.2V, the first specific discharge capacity is above 140mAh/g, the capacity surplus rate is above 85 percent after two hundred charged and discharged circulation. The specific capacity of the lithium manganese oxide which is prepared by the invention is high, the cycle performance is excellent and is applied widely to the lithium ion batteries such as: coin-type, square, cylindrical.
Description
Technical field
The invention relates to a kind of preparation method of lithium ion secondary battery anode material, especially about a kind of preparation method of spinel lithium manganese oxide of adulterated rich lithium.
Background technology
Lithium ion battery is widely used on the portable electric appts, and as the lithium ion battery core is its positive electrode material.At present, LiCoO
2, LiNiO
2And LiMn
2O
4Be considered to the most attractive positive electrode material, LiCoO
2And LiNiO
2Theoretical specific capacity be about 275 MAH/grams, actual specific capacity has about 140 MAH/grams, but LiCoO
2Material expensive, LiNiO
2Material preparation is difficulty relatively, and these two kinds of materials LiNiO particularly
2Under high pressure discharge oxygen, can produce potential safety hazard.LiMn
2O
4Although specific storage is lower, theoretical specific capacity is 148 MAH/grams, and actual specific capacity is 90-120 MAH/gram, and this material price is cheap, only is LiCoO
2About 1/10th, take off the MnO behind the lithium fully
2More stable, safety performance is good, so LiMn
2O
4Material has broad application prospects.
But because LiMn
2O
4The material lithium ion that some is lost in charge and discharge process has participated in the formation of negative terminal surface SEI (solid electrolyte interface) film, this a part of lithium ion is to move back in the positive electrode material again, therefore cause this material the first time loading capacity and for the second time loading capacity differ bigger.LiMn
2O
4Material belongs to spinel structure, and in this structure, lithium ion is arranged in eighth tetrahedron space, and this explanation also has more space can hold lithium ion.If in these spaces, hold more lithium ion, just can compensate the lithium ion disappearance that causes owing to the SEI film, thereby improve the specific storage of lithium manganese oxygen material.
In addition, because LiMn
2O
4In Mn
3+D
4Electronic configuration makes and the generation of ginger-Taylor (Jahn-Teller) effect causes LiMn
2O
4Structural instability, make LiMn
2O
4The capacity attenuation of material is fast, and cycle performance is poor.Simultaneously because Mn
3+Dissolving in ionogen and disproportionation have caused in the situation shorter deficiency in following work-ing life that is higher than 55 ℃.Overcoming these insufficient methods at present has: on the one hand to LiMn
2O
4Carry out surface-coated and parcel, material surface is not directly contacted with electrolyte solution, to reduce Mn
3+Dissolving and disproportionation.Be exactly to spinel LiMn on the other hand
2O
4Carry out negatively charged ion and cation doping,, make mn ion avoid d as far as possible with the valence state of change manganese and the content of manganese
4Electronic configuration is to reduce ginger-Taylor effect.
For example, CN 1458706A discloses a kind of anode material for lithium-ion batteries and preparation method thereof, and the chemical constitution of this material is Li
xMn
1-yM
yO
2, 0.5≤x≤1.5,0≤y≤0.5 wherein, M is any one among Cr, Co, Ni, Al, Ga, In, Tl, the Ti; Its preparation method comprised a kind of compound that contains lithium and a kind of manganiferous compound and a kind of compound that contains doping metals M mixed by suitable proportion, carried out solid state reaction in air atmosphere at 600-1000 ℃ of following roasting 12-36 hour.The compound that wherein contains lithium is selected from lithium nitrate, Lithium Acetate, lithium hydroxide and Quilonum Retard; Manganiferous compound is selected from manganous nitrate, manganese acetate, manganous carbonate, chemical manganese bioxide (CMD) and electrolytic manganese dioxide (EMD); The compound that contains doping metals M is its corresponding oxide compound, oxyhydroxide and salt.This material passes through at LiMn
2O
4The above-mentioned metal M of mixing in the material is improved cycle performance, make that anode material for lithium-ion batteries is 149-154 MAH/gram with the initial charge capacity that the electric current of 0.4-0.5C carries out constant current charge-discharge between 2.70-4.35 volt, loading capacity is 142-147 MAH/gram first, capability retention after the continuous current circulation 100 times is 84.5%, but the capability retention that circulates after 200 times is reduced to below 60%.Obviously, the cycle performance of the anode material for lithium-ion batteries that is made by aforesaid method can not satisfy actual needs.
It is Li that CN 1148738A discloses a kind of chemical constitution
xMn
2-yM
yO
4(1≤x≤2.1 wherein, 0.45≤y≤0.60, M is a divalent metal) anode material for lithium-ion batteries and preparation method thereof, this preparation method comprises solid reaction process and sol-gel method. wherein solid reaction process is included in 750-850 ℃ of following roasting lithium compound, manganic compound and metal M compound; Again 750-850 ℃ of following roasting through at least once the compacting after the material of roasting. sol-gel method comprises the inorganic salt with lithium, in oxyhydroxide and the organic acid salt one or more, the inorganic salt of manganese and in the organic acid salt one or more and contain the inorganic salt of M metal and a kind of several ethanol or the aqueous solution in the organic acid salt, add ammoniacal liquor and heating then, obtain the colloidal material, this colloidal material of roasting promptly gets lithium ion anode material. and the anode material for lithium-ion batteries electric current with 0.5C between the 2.70-4.2 volt that makes with aforesaid method carries out constant current charge-discharge, capability retention after the continuous current circulation 100 times is 80%, but the capability retention that circulates after 200 times is reduced to below 70%. and sol-gel method uses the organic acid salt price not only expensive but also have a potential safety hazard.
Summary of the invention
The objective of the invention is in order to overcome LiMn
2O
4The shortcoming of material cycle performance difference provides a kind of spinel lithium manganese oxide preparation methods of good cycle.
The invention provides a kind of preparation method of spinel lithium manganese oxide of adulterated rich lithium, this method comprises that compound, the manganiferous compound that will contain lithium and the compound that contains doping metals are even, roasting then, wherein, described roasting comprises one section roasting and two-stage calcination, described one section roasting comprises the evenly back roasting of compound that manganiferous compound, the compound that contains doping metals and a part is contained lithium, obtain one section product of roasting, described two-stage calcination comprises roasting after one section product of roasting and the remaining compound that contains lithium.
The present invention divides two stages to add by the lithium that will participate in formation lithium manganese oxygen, make the spinel lithium manganese oxide of the adulterated rich lithium that employing method provided by the invention makes have higher specific storage and excellent cycle performance as anode material for lithium-ion batteries, first discharge specific capacity is up to 140 MAH/grams, and circulating, capability retention can be up to about 85% after 200 times.
Embodiment
According to method provided by the invention, it is Li that the spinel lithium manganese oxide compound of described adulterated rich lithium is preferably chemical constitution
1+xMn
2-yM
yO
4The lithium manganese and oxygen compound, 0＜x≤0.1 wherein, 0＜y≤0.05, M is preferably selected from a kind of in the metal of II main group, III main group, IV main group and I-VIII subgroup, more preferably is selected from a kind of among Mg, Al, Fe, Ca, Cr, Sn, Ti, Zn, the Zr.
Wherein, the compound that contains lithium that adds in one section roasting, manganiferous compound and the compound that contains doping metals M are 1 with Li, Mn, M element molar ratio computing: (2-y): the x that y, the compound that contains lithium that adds in the two-stage calcination count the lithium-containing compound that adds in one section roasting with the elemental lithium mole doubly.X, y and Li
1+xMn
2-yM
yO
4In x and the numerical value of y identical respectively.
The described compound that contains compound, the manganiferous compound of lithium and contain doping metals can mix with dry powder form separately, also can in solvent, mix, preferably in solvent, mix, so both can guarantee that material is easier mixes, but also can avoid electrolytic manganese dioxide to catch fire.The weight of solvent is preferably compound, the manganiferous compound that contains lithium and the 1-50 of the compound gross weight that contains doping metals doubly, more preferably 1-30 doubly, more preferably 1-10 is doubly.
Further preferred described one-stage sintering product mixes in solvent with the compound that contains lithium, the 1-50 that the weight of solvent is preferably the compound that contains lithium and one-stage sintering product gross weight doubly, more preferably 1-30 doubly, more preferably 1-10 times.Described solvent can be that water, carbonatoms are the lower alcohol of 1-4 or their mixture.
Under the preferable case, after mixing, this method also comprises and will carry out one-stage sintering or bis sintering behind the removal of solvents again.The removal method of solvent can be direct volatilization, also can heated volatile, can also reduce pressure and remove, be the lower alcohol of 1-4 for water and carbonatoms, and the removal method of solvent preferably includes removes the above-mentioned mixture that mixes that contains solvent 80-200 ℃ of following stirring heating.
Under the preferable case, the preparation method of the spinel lithium manganese oxide compound of described adulterated rich lithium also comprises and will carry out bis sintering again after the pulverizing of one-stage sintering product, the screening.The one-stage sintering product that is preferably by the 100-300 mesh sieve carries out bis sintering with the compound that contains lithium.Can be behind one-stage sintering directly the one-stage sintering product be taken out and pulverize, pulverize after also can making the sintered product cooling again, described cooling can be directly cooling in air, also can be in sintering oven furnace cooling.The concrete operations of described pulverizing and screening have been conventionally known to one of skill in the art, do not repeat them here.
The condition of described one section roasting and two-stage calcination comprises that maturing temperature is preferably 750-900 ℃, and roasting time is preferably 8-15 hour.The condition of one section roasting and two-stage calcination can be identical or different.
Under the preferable case, the preparation method of the spinel lithium manganese oxide compound of described adulterated rich lithium also comprises and will pulverize and sieve after the cooling of two-stage calcination product.Refrigerative speed slowly cooled to below 100 ℃ the two-stage calcination product in 8-20 hour, more preferably be cooled to room temperature to 100 ℃.Described cooling can be carried out in the stoving oven of preparation two-stage calcination product, and the refrigerative mode is preferably two-stage calcination product furnace cooling in stoving oven.Described two-stage calcination product is placed in the stoving oven cools off specific storage and the cycle performance that helps further to improve the spinel lithium manganese oxide compound of described adulterated rich lithium with stoving oven.Therefore, cooling of the present invention is preferably two-stage calcination product furnace cooling in stoving oven, be cooled to be lower than 100 ℃ after again blow-on take out the two-stage calcination product and pulverize, sieve.Pulverize, the degree of screening is by the purposes of the spinel lithium manganese oxide compound of adulterated rich lithium and need decision.For example, when the spinel lithium manganese oxide compound of described adulterated rich lithium is used as cell positive material, generally select 100-300 purpose sieve for use, preferred 200 purposes sieve.
According to the present invention, because carbanion, hydroxide ion and nitrate ion can directly be removed in sintering process, and organolithium is not only expensive but also have potential safety hazard in sintering process, so the preferred described compound that contains lithium of the present invention is in Quilonum Retard, lithium hydroxide, the lithium nitrate one or more.Described manganiferous compound can be selected from one or more in manganous nitrate, manganese acetate, manganous carbonate, chemical manganese bioxide and the electrolytic manganese dioxide, for the proper density that has of the positive electrode material that guarantees to make behind the sintering is closed granularity, with the specific storage and the cycle life of further raising positive electrode material, the average particle diameter D of preferred described manganiferous compound
50Be the 4-10 micron.The described compound that contains doping metals M is selected from one or more in nitrate, acetate and the oxide compound of this doping metals M.M is preferably selected from a kind of in the metal of II main group, III main group, IV main group and I-VIII subgroup, more preferably is selected from a kind of among Mg, Al, Fe, Ca, Cr, Sn, Ti, Zn, the Zr.
The following examples will the present invention is further illustrated.
Embodiment 1
Present embodiment is used to illustrate the preparation method of the spinel lithium manganese oxide compound of adulterated rich lithium provided by the invention.
With 607.59 gram Quilonum Retards, 2873.71 gram electrolytic manganese dioxide (D
50=6 microns) and 8.47 gram Al
2O
3Mix in the deionized waters at 5000 grams,, obtain the one-stage sintering product in roasting 15 hours in 750 ℃ of muffle furnaces after 150 ℃ of oven dry.Directly in stove, take out this sintered product, pulverize and cross 200 mesh sieves then with airflow milling, get 2998.68 these screening things of gram and 6.07 and restrain Quilonum Retards and restrain in the alcohol 5000 and mix,, obtain the bis sintering product in roasting 15 hours in 750 ℃ of muffle furnaces after 100 ℃ of oven dry.With this sintered product furnace cooling 10 hours in muffle furnace, reduce to room temperature, take out afterwards with airflow milling and pulverized 200 mesh sieves, obtain 3500 and digest to learn and consist of Li
1.01Mn
1.99Al
0.01O
4The spinel lithium manganese oxide compound of adulterated rich lithium. verified the composition of above-claimed cpd with IRISAdvantange 1000ICP-AES type plasma emission spectrometer.
Embodiment 2
Present embodiment is used to illustrate the preparation method of the spinel lithium manganese oxide compound of adulterated rich lithium provided by the invention.
With 1103.91 gram lithium nitrates, 2851.67 gram electrolytic manganese dioxide (D
50=8 microns) and 19.98 gram magnesium oxide mix in the deionized waters at 10000 grams, in roasting 12 hours in 850 ℃ of muffle furnaces after 150 ℃ of oven dry, obtain the one-stage sintering product.Directly in stove, take out this sintered product, pulverize and cross 200 mesh sieves then with airflow milling, getting 2995.38 these screening things of gram and 44.15 restrains lithium nitrates and restrains in the mixed solvent of alcohol and deionized water (volume ratio 1: 1) 10000 and mix, in roasting 10 hours in 900 ℃ of muffle furnaces after 120 ℃ of oven dry, obtain the bis sintering product.With this sintered product furnace cooling 8 hours in muffle furnace, reduce to 60 ℃, take out afterwards with airflow milling and pulverized 200 mesh sieves, obtain 3640 and digest to learn and consist of Li
1.04Mn
1.97Al
0.03O
4The spinel lithium manganese oxide compound of adulterated rich lithium.Verified the composition of above-claimed cpd with IRIS Advantange 1000ICP-AES type plasma emission spectrometer.
Embodiment 3
Present embodiment is used to illustrate the preparation method of the spinel lithium manganese oxide compound of adulterated rich lithium provided by the invention.
With 18.71 gram lithium hydroxides, 577.45 gram Quilonum Retards, 2822.58 gram electrolytic manganese dioxide (D
50=8 microns) and 88.09 gram Cr
2O
3Mix in the alcohol at 20000 grams,, obtain the one-stage sintering product in roasting 10 hours in 900 ℃ of muffle furnaces after 100 ℃ of oven dry.Directly in stove, take out this sintered product, pulverize and cross 200 mesh sieves then with airflow milling, getting 2992.34 these screening things of gram and 11.22 gram lithium hydroxides, 34.62 restrains Quilonum Retards and restrains in the mixed solvent of alcohol and deionized water (volume ratio 1: 1) 20000 and mix, in roasting 12 hours in 800 ℃ of muffle furnaces after 120 ℃ of oven dry, obtain the bis sintering product.With this sintered product furnace cooling 12 hours in muffle furnace, reduce to room temperature, take out afterwards with airflow milling and pulverized 200 mesh sieves, obtain 3520 and digest to learn and consist of Li
1.06Mn
1.96Al
0.04O
4The spinel lithium manganese oxide compound of adulterated rich lithium.Verified the composition of above-claimed cpd with IRIS Advantange 1000ICP-AES type plasma emission spectrometer.
Embodiment 4
Present embodiment is used to illustrate the preparation method of the spinel lithium manganese oxide compound of adulterated rich lithium provided by the invention.
With 345.25 gram lithium nitrates, 184.97 gram Quilonum Retards, 119.91 gram lithium hydroxides, 2801.36 gram electrolytic manganese dioxide (D
50=10 microns) and 65.97 gram Fe
2O
3Mix in the deionized waters at 40000 grams,, obtain the one-stage sintering product in roasting 12 hours in 850 ℃ of muffle furnaces after 150 ℃ of oven dry.Directly in stove, take out this sintered product, pulverize and cross 200 mesh sieves then with airflow milling, getting 2988.53 these screening things of gram and 34.52 gram lithium nitrates, 18.49 gram Quilonum Retards, 11.99 restrains lithium hydroxides and restrains in the mixed solvent of alcohol and deionized water (volume ratio 1: 2) 40000 and mix, in roasting 10 hours in 900 ℃ of muffle furnaces after 120 ℃ of oven dry, obtain the bis sintering product.Taking-up is reduced to room temperature with the directly cooling 5 hours in air of this sintered product, pulverizes 200 mesh sieves with airflow milling then, obtains 3420 and digests to learn and consist of Li
1.10Mn
1.95Al
0.05O
4The spinel lithium manganese oxide compound of adulterated rich lithium.Verified the composition of above-claimed cpd with IRIS Advantange 1000ICP-AES type plasma emission spectrometer.
Comparative Examples 1
This Comparative Examples is used for illustrating the preparation method of prior art spinel type lithium manganese and oxygen compound.
With 613.66 gram Quilonum Retards, 2873.71 gram electrolytic manganese dioxide (D
50=6 microns) and 8.47 gram Al
2O
3Mix in the deionized waters at 15000 grams,, obtain sintered product in roasting 30 hours in 750 ℃ of muffle furnaces after 150 ℃ of oven dry.Directly take out this sintered product in the stove, cooling was reduced to room temperature after 5 hours in air, pulverized 200 mesh sieves with airflow milling then, obtained 3200 and digested to learn and consist of Li
1.01Mn
1.99Al
0.01O
4The spinel lithium manganese oxide compound of adulterated rich lithium.Verified the composition of above-claimed cpd with IRISAdvantange 1000ICP-AES type plasma emission spectrometer.
Embodiment 5-8
The spinel lithium manganese oxide compound of getting the adulterated rich lithium that 3000 gram embodiment 1-4 make respectively restrains the graphitized carbon black dry blending with 120, the polyvinylidene difluoride (PVDF) N that adds 750 grams, 8 weight % then, after stirring in stirrer, N-dimethyl pyrrolidone solution is coated on the aluminium foil, make positive pole, wherein the content of the spinel lithium manganese oxide compound of adulterated rich lithium is 3.80 grams; With the synthetic graphite is negative pole, is diaphragm paper with Celgard 2700, with the LiPF of 1 mol
6For electrolytic solution (EC+DMC+DEC (volume ratio 1: 1: 1) is a solvent), be assembled into square battery.Above-mentioned battery electric current with 0.5C between the 3.0-4.2 volt is discharged and recharged, record the Li that embodiment 1 makes
1.01Mn
1.99Al
0.01O
4The partial volume capacity of material is 534.83 MAHs, specific storage is 140.74 MAH/grams, loading capacity after the 1st circulation is 532.56 MAHs, and the loading capacity after the 200th circulation is 454.17 MAHs, and 200 times circulation back capacity surplus ratio is 85.28%; The Li that embodiment 2 makes
1.04Mn
1.97Mg
0.03O
4The partial volume capacity of material is 537.94 MAHs, specific storage is 141.56 MAH/grams, loading capacity after the 1st circulation is 533.94 MAHs, and the loading capacity after the 200th circulation is 454.28 MAHs, and 200 times circulation back capacity surplus ratio is 85.08%; The Li that embodiment 3 makes
1.06Mn
1.96Cr
0.04O
4The partial volume capacity of material is 539.40 MAHs, specific storage is 141.95 MAH/grams, loading capacity after the 1st circulation is 537.75 MAHs, and the loading capacity after the 200th circulation is 458.32 MAHs, and 200 times circulation back capacity surplus ratio is 85.23%; The Li that embodiment 4 makes
1.1Mn
1.95Fe
0.05O
4The partial volume capacity of material is 539.56 MAHs, specific storage is 141.94 MAH/grams, loading capacity after the 1st circulation is 537.83 MAHs, and the loading capacity after the 200th circulation is 436.30 MAHs, and 200 times circulation back capacity surplus ratio is 81.12%.
Comparative Examples 2
The spinel lithium manganese oxide compound of getting the 3000 adulterated rich lithiums that make of gram Comparative Examples 1 restrains the graphitized carbon black dry blending with 120, the polyvinylidene difluoride (PVDF) N that adds 750 grams, 8 weight % then, after stirring in stirrer, N-dimethyl pyrrolidone solution is coated on the aluminium foil, make positive pole, wherein the content of the spinel lithium manganese oxide compound of adulterated rich lithium is 3.80 grams; With the synthetic graphite is negative pole, is diaphragm paper with Celgard2700, with the LiPF of 1 mol
6For electrolytic solution (EC+DMC+DEC (volume ratio 1: 1: 1) is a solvent), be assembled into square battery.Above-mentioned battery electric current with 0.5C between the 3.0-4.2 volt is discharged and recharged, record the Li that Comparative Examples 1 makes
10.1Mn
1.99Al
0.01O
4The partial volume capacity be 493.58 MAHs, specific storage is 129.89 MAH/grams, the loading capacity after the 1st circulation is 487.33 MAHs, the loading capacity after 200 circulations is 348.27 MAHs, 200 times circulation back capacity surplus ratio is 70.56%.
Claims (10)
1. the preparation method of the spinel lithium manganese oxide of an adulterated rich lithium, this method comprises and will contain the compound of lithium, manganiferous compound is even with the compound that contains doping metals, roasting then, it is characterized in that, described roasting comprises one section roasting and two-stage calcination, described one section roasting comprises manganiferous compound, the compound and a part of evenly back roasting of compound that contains lithium that contain doping metals, obtain one section product of roasting, described two-stage calcination comprises roasting after one section product of roasting and the remaining compound that contains lithium, wherein, the described compound that contains lithium, manganiferous compound mixes in solvent with the compound that contains doping metals, and the weight of solvent is the compound that contains lithium, the 1-50 of manganiferous compound and the compound gross weight that contains doping metals doubly.
2. method according to claim 1, wherein, the spinel lithium manganese oxide compound of described adulterated rich lithium is that chemical constitution is Li
1+xMn
2-yM
yO
4The lithium manganese and oxygen compound; The add-on that contains compound, the manganiferous compound of lithium during one section roasting and contain the compound of doping metals counts 1 with Li, Mn, M element mole: (2-y): the x when y, the compound that contains lithium that adds during two-stage calcination count one section roasting with the elemental lithium mole doubly; 0＜x≤0.1,0＜y≤0.05 wherein, M is selected from a kind of in the metal of II main group, III main group, IV main group and I-VIII subgroup.
3. method according to claim 2, wherein, M is selected from a kind of among Mg, Al, Fe, Ca, Cr, Sn, Ti, Zn, the Zr.
4. method according to claim 1, wherein, described one section product of roasting mixes in solvent with the compound that contains lithium, and the weight of solvent is to contain the compound of lithium and 1-50 times of one section product of roasting gross weight.
5. method according to claim 4, wherein, described solvent is that water, carbonatoms are the lower alcohol of 1-4 or their mixture.
6. method according to claim 1, wherein, the condition of described one section roasting and two-stage calcination comprises that maturing temperature is 750-900 ℃, roasting time is 8-15 hour.
7. method according to claim 1, wherein, this method comprises that also refrigerative speed slowly cooled to below 100 ℃ the two-stage calcination product in 8-20 hour with the cooling of two-stage calcination product.
8. method according to claim 7, wherein, described cooling is carried out in the stoving oven of preparation two-stage calcination product, and the refrigerative mode is with two-stage calcination product furnace cooling in stoving oven.
9. method according to claim 1 and 2, wherein, the described compound that contains lithium is selected from one or more in Quilonum Retard, lithium hydroxide, the lithium nitrate, and described manganiferous compound is selected from one or more in manganous nitrate, manganese acetate, manganous carbonate, chemical manganese bioxide and the electrolytic manganese dioxide; The described compound that contains doping metals is selected from one or more in nitrate, acetate and the oxide compound of this doping metals, and described doping metals is selected from a kind of among Mg, Al, Fe, Ca, Cr, Sn, Ti, Zn, the Zr.
10. method according to claim 9, wherein, the average particle diameter D of described manganiferous compound
50Be the 4-10 micron.
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| CN110422890A (en) * | 2019-06-25 | 2019-11-08 | 当升科技(常州)新材料有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion cell positive and lithium ion battery |
| CN113184923A (en) * | 2021-04-29 | 2021-07-30 | 昆山宝创新能源科技有限公司 | Preparation method of niobium modified lithium-rich manganese-based material, positive electrode material and lithium ion battery |
| WO2023115289A1 (en) * | 2021-12-21 | 2023-06-29 | 昶联金属材料应用制品(广州)有限公司 | Nickel-rich material and preparation method therefor, positive electrode plate, battery and electric equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1455466A (en) * | 2003-04-30 | 2003-11-12 | 杨永平 | Spinel lithium manganate with stable structure for lithium ion cell and manufacturing method thereof |
| CN101070191A (en) * | 2006-05-08 | 2007-11-14 | 上海川那电池制造有限公司 | Process for preparing lithium ion cell positive pole material |
-
2006
- 2006-08-04 CN CN200610109528A patent/CN101117234B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1455466A (en) * | 2003-04-30 | 2003-11-12 | 杨永平 | Spinel lithium manganate with stable structure for lithium ion cell and manufacturing method thereof |
| CN101070191A (en) * | 2006-05-08 | 2007-11-14 | 上海川那电池制造有限公司 | Process for preparing lithium ion cell positive pole material |
Non-Patent Citations (2)
| Title |
|---|
| 王志兴等.Al 掺杂对锰酸锂结构与性能的影响.电池35 2.2005,35(2),119-120. |
| 王志兴等.Al 掺杂对锰酸锂结构与性能的影响.电池35 2.2005,35(2),119-120. * |
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