CN103490063A - Preparation method for modified lithium cobalt oxide capable of being recycled at high cut-off voltage - Google Patents
Preparation method for modified lithium cobalt oxide capable of being recycled at high cut-off voltage Download PDFInfo
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- CN103490063A CN103490063A CN201310412847.6A CN201310412847A CN103490063A CN 103490063 A CN103490063 A CN 103490063A CN 201310412847 A CN201310412847 A CN 201310412847A CN 103490063 A CN103490063 A CN 103490063A
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- 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
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Abstract
The present invention relates to a preparation method for modified lithium cobalt oxide capable of being recycled at a high cut-off voltage. The preparation method comprises: preparing a manganese-doped lithium cobalt oxide material according to the conventional method in the field, mixing the obtained lithium cobalt oxide half finished product and an additive such as magnesium oxide, alumina, titanium dioxide, silica, tin dioxide, zirconium dioxide, cerium dioxide and the like according to a certain ratio, calcining for 5-20 h at a temperature of 500-1100 DEG C, and grinding to obtain the modified lithium cobalt oxide product. The preparation method has the following characteristics that: operations are simple, the process is easy to control, cycle performances of the synthesized product are significantly more excellent than cycle performances of the unmodified product at the high cut-off voltage so as to increase the cut-off voltage of the lithium ion battery, and the preparation method is suitable for industrialization manufacturing of lithium ion battery positive electrode materials.
Description
Technical field
The present invention relates to the anode material for lithium-ion batteries field, particularly a kind of preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage.
Background technology
Operating voltage is high, specific energy is large, self discharge is little owing to having for lithium ion battery, have extended cycle life, lightweight, memory-less effect, the characteristics such as low in the pollution of the environment, the ready-made emphasis for the research and development of countries in the world power supply.Cobalt acid lithium relies on that its good reversibility, discharge capacity are high, the good stability of voltage and the advantage such as production technology is simple, in occupation of the main status in anode material for lithium-ion batteries market.
Along with smart mobile phone, panel computer, super this grade of utmost point 3C electronic product development, electronic product manufacturer requires more and more higher to the energy density of cobalt acid lithium battery.One of at present main solution is to improve the charge cutoff voltage of cobalt acid lithium, this measure can increase substantially specific capacity and the specific energy density of battery, shortcoming is to cause the excessively de-lithium of cobalt acid lithium, cause the unstable of structure, the loss of oxygen loss reaction and cobalt occurs, capacity can be decayed, and causes cycle performance significantly to be decayed.Although the raising cut-ff voltage, can improve cobalt acid lithium specific energy density, can cause the material internal structure to be caved in, the structural stability variation, the cycle performance variation, therefore, the battery charge cutoff voltage that the cobalt acid lithium of generally take at present is positive electrode is still 4.3V.The present invention is for solving the cobalt acid lithium method that cycle performance variation problem provides under high cut-ff voltage.
Summary of the invention
In order to address the above problem, the invention provides a kind of preparation method of the modified cobalt acid lithium material that can recycle under high cut-ff voltage.
The present invention relates to a kind of good modified cobalt acid lithium of performance that recycles under high cut-ff voltage, it comprises that step is as follows:
1) prepare cobalt acid lithium by this area conventional method;
2) cobalt of gained in step 1) acid lithium is mixed according to a certain percentage with additive, under 500 ℃～1100 ℃, calcine 5h～20h, cooling, grinding, obtain described modified cobalt acid lithium.
Wherein, the cobalt acid lithium prepared in step 1) can be the cobalt acid lithium material LiCo of manganese doping
1-xmn
xo
2, 0≤x≤0.15 wherein.
The cobalt acid lithium material LiCo for preparing this manganese doping
1-xmn
xo
2method be the ability conventional method, specifically comprise the steps:
A) by solubility cobalt salt and soluble manganese salt, according to the mol ratio of Co:Mn, be (1-x): x, 0≤x≤0.15 wherein, the mixed aqueous solution I that to be mixed with the metal ion total concentration be 0.5M～3.0M;
B) by the sodium hydroxide solution of ammoniacal liquor and 0.5M～5.0M according to volume ratio 1:(3～20) ratio be mixed with the mixed solution II;
C) by mixed aqueous solution I and the step 2 of step a) preparation) the mixed solution II of preparation evenly joins in reactor and reacted continuously, the pH value of controlling reaction is 9.0～12.0, reaction temperature is 30 ℃～100 ℃, stirred in the time of reaction, continued to stir 0.5h～10h after reinforced the end;
D) mixture of step c) gained is carried out to suction filtration, deionized water washing, drying, obtain the spherical or spherical presoma of class;
E) by step d) gained presoma with lithium carbonate in Li:(Co+Mn) molar ratio is (0.9～1.1): 1 ratio mixes, and under 900 ℃～1100 ℃, calcines 5h～20h, cooling, grind, and obtains the semi-finished product of cobalt acid lithium.
Described solubility cobalt salt is one or both the mixture in cobaltous sulfate or cobalt nitrate; Described soluble manganese salt is one or both the mixture in manganese sulfate or manganese nitrate salt, uses the purity of solubility cobalt salt and manganese salt, NaOH and ammoniacal liquor pure for analyzing.Described additive be magnesium oxide, aluminium oxide, titanium dioxide, silicon dioxide, tin ash, zirconium dioxide, ceria etc. one or more, the part by weight that accounts for step 1) gained cobalt acid lithium is less than or equal to 1.0% for being greater than 0%; Described additive specific area is not less than 10m
2/ g.Final modified product: the middle particle diameter D50 of described modified cobalt acid lithium is 5.0 μ m～25.0 μ m, and specific area is 0.05m
2/ g～0.8m
2/ g, pH is 10.0～11.5.
The relative prior art of the present invention has following advantage:
The present invention introduces manganese element by coprecipitation and cobalt acid lithium is carried out bulk phase-doped, and cobalt element and manganese element are mixed on atomic level, and cobalt acid lithium granule interior comparison of ingredients is even.Manganese element is in charge and discharge process, maintaining the tetravalence chemical valence does not change, can play the effect of supporting cobalt acid lithium structure, suppress the expansion of cell parameter in cobalt acid lithium charge and discharge process simultaneously, reduce transformation stress, improve the stability of cobalt acid lithium structure, what increase cobalt acid lithium effectively discharges and recharges number of times, increase access times, effectively improved cycle performance
Next, the present invention adopts and adds the additive that specific area is large, and the formation one deck coating material at cobalt acid lithium surface uniform, can effectively reduce the oxygen loss reaction that cobalt acid lithium reaches between the two with contacting of electrolyte, suppresses the dissolving of cobalt ions simultaneously.
Products therefrom of the present invention is (4.6V) under high cut-ff voltage, and cycle performance is greatly improved than unmodified cobalt acid lithium, and the available number of times that discharges and recharges increases, and extend the useful life of battery.In addition, the battery that adopts modified cobalt acid lithium to prepare, compare with the battery that adopts conventional cobalt acid lithium to prepare, the cut-ff voltage used is higher, under battery volume the same terms, the capacity of cell is larger, can extend greatly stand-by time and the service time of 3C electronic product.
Simultaneously, synthetic method of the present invention, simple to operate, process is easy to control, and can increase substantially the cycle performance of cobalt acid lithium product under high cut-ff voltage simultaneously, is suitable for carrying out suitability for industrialized production.
The accompanying drawing explanation
Fig. 1 is the cycle performance comparison diagram of comparative example and embodiment.
Embodiment
The preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage the present invention below in conjunction with embodiment is described in more detail.And protection scope of the present invention not only is confined to following examples.The those of ordinary skill of described technical field, according to above disclosure of the present invention, all can be realized purpose of the present invention.
Comparative example
The 1mol cobaltous sulfate is made into to the 1000ml mixed solution; The sodium hydroxide solution of ammoniacal liquor and 2M is made to mixed solution 1100ml according to the ratio of volume ratio 1:10.Identical speed by above-mentioned two kinds of solution with 3ml/min joins in the reactor of 5L, and controlling reaction temperature is 55 ℃, and controlling the pH value is 11.5, and constantly stirs until reinforced the end continues to stir 0.5 hour.By the pitchy that obtains precipitation filtered, the deionized water washing, drying obtains the hydroxyl oxidize cobalt precursor.Be that 1.04:1 ratio mix according to Li with the mol ratio of Co with lithium carbonate by above-mentioned presoma, under 1000 ℃, calcine 10h, cooling grinding obtains semi-finished product; The gained semi-finished product are mixed, under 900 ℃, calcine 10h, cooling grinding obtains final products.In 3.0V～4.6V voltage range, carry out the charge and discharge cycles test under 2.0mA/cm2 current density condition, after 50 circulations, capability retention is 35%.
Embodiment 1
0.95mol cobaltous sulfate and 0.05mol manganese sulfate are made into to the 1000ml mixed solution; The sodium hydroxide solution of ammoniacal liquor and 2M is made to mixed solution 1100ml according to the ratio of volume ratio 1:10.Identical speed by above-mentioned two kinds of solution with 3.0ml/min joins in the reactor of 5L, and controlling reaction temperature is 55 ℃, and controlling the pH value is 11.5, and constantly stirs until reinforced the end continues to stir 0.5 hour.The pitchy precipitation obtained is filtered, the deionized water washing, drying obtains manganese doping hydroxyl oxidize cobalt precursor.Be that 1.04:1 ratio mix according to Li with the mol ratio of (Co+Mn) with lithium carbonate by above-mentioned presoma, under 1000 ℃, calcine 10h, cooling grinding obtains cobalt acid lithium semi-finished product; The gained semi-finished product are mixed with the silicon dioxide of its quality 0.5%, under 900 ℃, calcine 10h, cooling grinding obtains final modified cobalt acid lithium product.In 3.0V～4.6V voltage range, carry out the charge and discharge cycles test under 2.0mA/cm2 current density condition, after 50 circulations, capability retention is 45%.
Embodiment 2
0.95mol cobaltous sulfate and 0.05mol manganese sulfate are made into to the 1000ml mixed solution; The sodium hydroxide solution of ammoniacal liquor and 2M is made to mixed solution 1100ml according to the ratio of volume ratio 1:10.Identical speed by above-mentioned two kinds of solution with 3.0ml/min joins in the reactor of 5L, and controlling reaction temperature is 55 ℃, and controlling the pH value is 11.5, and constantly stirs until reinforced the end continues to stir 0.5 hour.The pitchy precipitation obtained is filtered, the deionized water washing, drying obtains manganese doping hydroxyl oxidize cobalt precursor.Be that 1.04:1 ratio mix according to Li with the mol ratio of (Co+Mn) with lithium carbonate by above-mentioned presoma, under 1000 ℃, calcine 10h, cooling grinding obtains cobalt acid lithium semi-finished product; The magnesium oxide of gained semi-finished product and its quality 0.5%, by mixing, is calcined 10h under 900 ℃, and cooling grinding obtains final modified cobalt acid lithium product.In 3.0V～4.6V voltage range, carry out the charge and discharge cycles test under 2.0mA/cm2 current density condition, after 50 circulations, capability retention is 50%.
Embodiment 3
0.95mol cobaltous sulfate and 0.05mol manganese sulfate are made into to the 1000ml mixed solution; The sodium hydroxide solution of ammoniacal liquor and 2M is made to mixed solution 1100ml according to the ratio of volume ratio 1:10.Identical speed by above-mentioned two kinds of solution with 3.0ml/min joins in the reactor of 5L, and controlling reaction temperature is 55 ℃, and controlling the pH value is 11.5, and constantly stirs until reinforced the end continues to stir 0.5 hour again.The pitchy precipitation obtained is filtered, the deionized water washing, drying obtains manganese doping hydroxyl oxidize cobalt precursor.Be that 1.04:1 ratio mix according to Li with the mol ratio of (Co+Mn) with lithium carbonate by above-mentioned presoma, under 1000 ℃, calcine 10h, cooling grinding obtains cobalt acid lithium semi-finished product; The gained semi-finished product mix with the aluminium oxide of its quality 0.5%, under 900 ℃, calcine 10h, and cooling grinding obtains final modified cobalt acid lithium product.In 3.0V～4.6V voltage range, carry out the charge and discharge cycles test under 2.0mA/cm2 current density condition, after 50 circulations, capability retention is 52%.
Embodiment 4
0.95mol cobaltous sulfate and 0.05mol manganese sulfate are made into to the 1000ml mixed solution; The sodium hydroxide solution of ammoniacal liquor and 2M is made to mixed solution 1100ml according to the ratio of volume ratio 1:10.Identical speed by above-mentioned two kinds of solution with 3.0ml/min joins in the reactor of 5L, and controlling reaction temperature is 55 ℃, and controlling the pH value is 11.5, and constantly stirs until reinforced the end continues to stir 0.5 hour.The pitchy precipitation obtained is filtered, the deionized water washing, drying obtains manganese doping hydroxyl oxidize cobalt precursor.Be that 1.04:1 ratio mix according to Li with the mol ratio of (Co+Mn) with lithium carbonate by above-mentioned presoma, under 1000 ℃, calcine 10h, cooling grinding obtains cobalt acid lithium semi-finished product; The gained semi-finished product mix with the titanium dioxide of its quality 0.5%, under 900 ℃, calcine 10h, and cooling grinding obtains final modified cobalt acid lithium product.In 3.0V～4.6V voltage range, carry out the charge and discharge cycles test under 2.0mA/cm2 current density condition, after 50 circulations, capability retention is 62%.
Embodiment 5
0.95mol cobaltous sulfate and 0.05mol manganese sulfate are made into to the 1000ml mixed solution; The sodium hydroxide solution of ammoniacal liquor and 2M is made to mixed solution 1100ml according to the ratio of volume ratio 1:10.Identical speed by above-mentioned two kinds of solution with 3.0ml/min joins in the reactor of 5L, and controlling reaction temperature is 55 ℃, and controlling the pH value is 11.5, and constantly stirs until reinforced the end continues to stir 0.5 hour.The pitchy precipitation obtained is separated, filtered, the deionized water washing, drying obtains manganese doping hydroxyl oxidize cobalt precursor.Be that 1.04:1 ratio mix according to Li with the mol ratio of (Co+Mn) with lithium carbonate by above-mentioned presoma, under 1000 ℃, calcine 10h, cooling grinding obtains cobalt acid lithium semi-finished product; The gained semi-finished product mix with the zirconium dioxide of its quality 0.5%, under 900 ℃, calcine 10h, and cooling grinding obtains final modified cobalt acid lithium product.In 3.0V～4.6V voltage range, carry out the charge and discharge cycles test under 2.0mA/cm2 current density condition, after 50 circulations, capability retention is 55%.
Embodiment 6
0.95mol cobaltous sulfate and 0.05mol manganese sulfate are made into to the 1000ml mixed solution; The sodium hydroxide solution of ammoniacal liquor and 2M is made to mixed solution 1100ml according to the ratio of volume ratio 1:10.Identical speed by above-mentioned two kinds of solution with 3.0ml/min joins in the reactor of 5L, and controlling reaction temperature is 55 ℃, and controlling the pH value is 11.5, and constantly stirs until reinforced the end continues to stir 0.5 hour.The pitchy precipitation obtained is separated, filtered, the deionized water washing, drying obtains manganese doping hydroxyl oxidize cobalt precursor.Be that 1.04:1 ratio mix according to Li with the mol ratio of (Co+Mn) with lithium carbonate by above-mentioned presoma, under 1000 ℃, calcine 10h, cooling grinding obtains cobalt acid lithium semi-finished product; The gained semi-finished product mix with the ceria of its quality 0.5%, under 900 ℃, calcine 10h, and cooling grinding obtains final modified cobalt acid lithium product.In 3.0V～4.6V voltage range, carry out the charge and discharge cycles test under 2.0mA/cm2 current density condition, after 50 circulations, capability retention is 54%.
Embodiment 7
0.95mol cobaltous sulfate and 0.05mol manganese sulfate are made into to the 1000ml mixed solution; The sodium hydroxide solution of ammoniacal liquor and 2M is made to mixed solution 1100ml according to the ratio of volume ratio 1:10.Identical speed by above-mentioned two kinds of solution with 3.0ml/min joins in the reactor of 5L, and controlling reaction temperature is 55 ℃, and controlling the pH value is 11.5, and constantly stirs until reinforced the end continues to stir 0.5 hour.The pitchy precipitation obtained is separated, filtered, the deionized water washing, drying obtains manganese doping hydroxyl oxidize cobalt precursor.Be that 1.04:1 ratio mix according to Li with the mol ratio of (Co+Mn) with lithium carbonate by above-mentioned presoma, under 1000 ℃, calcine 10h, cooling grinding obtains cobalt acid lithium semi-finished product; The gained semi-finished product mix with the tin ash of its quality 0.5%, under 900 ℃, calcine 10h, and cooling grinding obtains final modified cobalt acid lithium product.In 3.0V～4.6V voltage range, carry out the charge and discharge cycles test under 2.0mA/cm2 current density condition, after 50 circulations, capability retention is 50%.
Comparative example and comparative example, adopt the cobalt acid lithium of the synthetic modified cobalt acid lithium of the inventive method than non-modified, and its cycle performance under high cut-ff voltage is greatly enhanced.
Claims (9)
1. the preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage is characterized in that the step of described method is as follows:
1) prepare cobalt acid lithium;
2) cobalt of gained in step 1) acid lithium is mixed according to a certain percentage with additive, under 500 ℃～1100 ℃, calcine 5h～20h, cooling, grinding, obtain described modified cobalt acid lithium.
2. the preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage as claimed in claim 1, is characterized in that described cobalt acid lithium prepared by step 1) is the cobalt acid lithium material LiCo that manganese adulterates
1-xmn
xo
2, 0≤x≤0.15 wherein.
3. the preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage as claimed in claim 1 or 2, is characterized in that step 1) specifically comprises the steps:
A) by solubility cobalt salt and soluble manganese salt, according to the mol ratio of Co:Mn, be (1-x): x, 0≤x≤0.15 wherein, the mixed aqueous solution I that to be mixed with the metal ion total concentration be 0.5M～3.0M;
B) by the sodium hydroxide solution of ammoniacal liquor and 0.5M～5.0M according to volume ratio 1:(3～20) ratio be mixed with the mixed solution II;
C) the mixed solution II of the mixed aqueous solution I of step a) preparation and step b) preparation is evenly joined in reactor and reacted continuously simultaneously, the pH value of controlling reaction is 9～12, reaction temperature is 30 ℃～100 ℃, stirred in the time of reaction, after reinforced the end, keep temperature to continue to stir 0.5h～10h;
D) mixture of step c) gained is carried out to suction filtration, deionized water washing, drying, obtain the spherical or spherical presoma of class;
E) by step d) gained presoma with lithium carbonate in Li:(Co+Mn) molar ratio is (0.9～1.1): 1 ratio mixes, and under 900 ℃～1100 ℃, calcines 5h～20h, cooling, grind the semi-finished product that obtain cobalt acid lithium.
4. the preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage as claimed in claim 3, is characterized in that described solubility cobalt salt is one or both the mixture in cobaltous sulfate or cobalt nitrate; Described soluble manganese salt is one or both the mixture in manganese sulfate or manganese nitrate salt.
5. the preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage as claimed in claim 3, is characterized in that the purity of described solubility cobalt salt, soluble manganese salt, NaOH and ammoniacal liquor is pure for analyzing.
6. the preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage as claimed in claim 1, is characterized in that described additive is one or more in magnesium oxide, aluminium oxide, titanium dioxide, silicon dioxide, tin ash, zirconium dioxide, in ceria.
7. the preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage as claimed in claim 1, it is characterized in that: the part by weight that described additive accounts for step 1) gained cobalt acid lithium is less than or equal to 1.0% for being greater than 0%.
8. the preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage as claimed in claim 1, it is characterized in that: described additive specific area is not less than 10m
2/ g.
9. the preparation method of the modified cobalt acid lithium that can recycle under high cut-ff voltage as claimed in claim 1, is characterized in that the middle particle diameter D of the described modified cobalt acid of final modified product lithium
50be 5.0 μ m～25.0 μ m, specific area is 0.05m
2/ g～0.8m
2/ g, pH is 10.0～11.5.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355889A (en) * | 2015-11-28 | 2016-02-24 | 西安瑟福能源科技有限公司 | High-voltage high-magnification lithium ion battery |
| CN109256531A (en) * | 2017-07-14 | 2019-01-22 | 中国科学院宁波材料技术与工程研究所 | Doping cobalt acid lithium and its preparation method and application with compound coating layer |
| CN111029552A (en) * | 2019-12-24 | 2020-04-17 | 天津巴莫科技有限责任公司 | High-voltage high-rate lithium cobalt oxide cathode material and preparation method thereof |
| CN111081987A (en) * | 2018-10-18 | 2020-04-28 | 湖南杉杉能源科技股份有限公司 | Lithium cobaltate cathode material of lithium ion battery with voltage of more than 4.45V and preparation method thereof |
| CN111342042A (en) * | 2016-08-01 | 2020-06-26 | 宁德新能源科技有限公司 | Positive electrode material and preparation method thereof, positive electrode piece and lithium ion battery |
| CN112582598A (en) * | 2020-11-23 | 2021-03-30 | 昆明理工大学 | Short-range regeneration synergistic high-voltage modification method for waste lithium cobalt oxide positive electrode material |
| CN113149083A (en) * | 2016-03-14 | 2021-07-23 | 苹果公司 | Cathode active material for lithium ion battery |
| WO2022157601A1 (en) * | 2021-01-22 | 2022-07-28 | 株式会社半導体エネルギー研究所 | Production method for positive electrode active material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004047437A (en) * | 2002-05-16 | 2004-02-12 | Matsushita Electric Ind Co Ltd | Positive electrode activator for nonaqueous electrolyte secondary battery, and manufacturing method of the same |
| CN101719546A (en) * | 2009-11-26 | 2010-06-02 | 上海大学 | Method for preparing lithium ion battery anode material doped with nanometer oxide |
| CN102344173A (en) * | 2011-10-25 | 2012-02-08 | 中信大锰矿业有限责任公司 | Method for producing lithium cobaltite by preparing hydroxyl trivalent cobalt oxide through wet chemical reaction |
| CN103236541A (en) * | 2013-04-12 | 2013-08-07 | 中信国安盟固利电源技术有限公司 | Method for improving storage performance of lithium cobalt oxide at high voltage and high temperature |
-
2013
- 2013-09-11 CN CN201310412847.6A patent/CN103490063A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004047437A (en) * | 2002-05-16 | 2004-02-12 | Matsushita Electric Ind Co Ltd | Positive electrode activator for nonaqueous electrolyte secondary battery, and manufacturing method of the same |
| CN101719546A (en) * | 2009-11-26 | 2010-06-02 | 上海大学 | Method for preparing lithium ion battery anode material doped with nanometer oxide |
| CN102344173A (en) * | 2011-10-25 | 2012-02-08 | 中信大锰矿业有限责任公司 | Method for producing lithium cobaltite by preparing hydroxyl trivalent cobalt oxide through wet chemical reaction |
| CN103236541A (en) * | 2013-04-12 | 2013-08-07 | 中信国安盟固利电源技术有限公司 | Method for improving storage performance of lithium cobalt oxide at high voltage and high temperature |
Non-Patent Citations (4)
| Title |
|---|
| 吴宇平等编著: "《绿色电源材料》", 31 July 2008, article ""氧化钴锂的包覆"", pages: 28 * |
| 吴宇平等编著: "《锂离子电池-应用与实践》", 31 December 2011, article ""氧化钴锂的包覆"", pages: 108 * |
| 汤宏伟等: ""LiCo1-xMxO2的循环伏安性能研究"", 《河南师范大学学报》, vol. 33, no. 2, 31 May 2005 (2005-05-31) * |
| 赵黎明等: ""锰掺杂钴酸锂 LiMnxCo1-xO2的性能研究"", 《电池工业》, vol. 12, no. 2, 30 April 2007 (2007-04-30) * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105355889A (en) * | 2015-11-28 | 2016-02-24 | 西安瑟福能源科技有限公司 | High-voltage high-magnification lithium ion battery |
| CN105355889B (en) * | 2015-11-28 | 2018-02-23 | 西安瑟福能源科技有限公司 | A kind of high voltage high multiplying power lithium ion battery |
| CN113149083A (en) * | 2016-03-14 | 2021-07-23 | 苹果公司 | Cathode active material for lithium ion battery |
| CN111342042A (en) * | 2016-08-01 | 2020-06-26 | 宁德新能源科技有限公司 | Positive electrode material and preparation method thereof, positive electrode piece and lithium ion battery |
| CN109256531A (en) * | 2017-07-14 | 2019-01-22 | 中国科学院宁波材料技术与工程研究所 | Doping cobalt acid lithium and its preparation method and application with compound coating layer |
| CN109256531B (en) * | 2017-07-14 | 2021-09-14 | 中国科学院宁波材料技术与工程研究所 | Doped lithium cobaltate with composite coating layer and preparation method and application thereof |
| CN111081987A (en) * | 2018-10-18 | 2020-04-28 | 湖南杉杉能源科技股份有限公司 | Lithium cobaltate cathode material of lithium ion battery with voltage of more than 4.45V and preparation method thereof |
| CN111081987B (en) * | 2018-10-18 | 2021-08-31 | 湖南杉杉能源科技股份有限公司 | Lithium cobaltate cathode material of lithium ion battery with voltage of more than 4.45V and preparation method thereof |
| CN111029552A (en) * | 2019-12-24 | 2020-04-17 | 天津巴莫科技有限责任公司 | High-voltage high-rate lithium cobalt oxide cathode material and preparation method thereof |
| CN111029552B (en) * | 2019-12-24 | 2021-07-13 | 天津巴莫科技有限责任公司 | High-voltage high-rate lithium cobalt oxide cathode material and preparation method thereof |
| CN112582598A (en) * | 2020-11-23 | 2021-03-30 | 昆明理工大学 | Short-range regeneration synergistic high-voltage modification method for waste lithium cobalt oxide positive electrode material |
| WO2022157601A1 (en) * | 2021-01-22 | 2022-07-28 | 株式会社半導体エネルギー研究所 | Production method for positive electrode active material |
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