CN102583583A - Cathode material of manganese, cobalt and lithium oxidate for lithium ion battery and preparation method of cathode material - Google Patents

Cathode material of manganese, cobalt and lithium oxidate for lithium ion battery and preparation method of cathode material Download PDF

Info

Publication number
CN102583583A
CN102583583A CN2012100636605A CN201210063660A CN102583583A CN 102583583 A CN102583583 A CN 102583583A CN 2012100636605 A CN2012100636605 A CN 2012100636605A CN 201210063660 A CN201210063660 A CN 201210063660A CN 102583583 A CN102583583 A CN 102583583A
Authority
CN
China
Prior art keywords
lithium
ion battery
lithium ion
preparation
cathode material
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
Application number
CN2012100636605A
Other languages
Chinese (zh)
Other versions
CN102583583B (en
Inventor
李莉萍
罗冬
余创
关翔锋
李广社
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Institute of Research on the Structure of Matter of CAS
Original Assignee
Fujian Institute of Research on the Structure of Matter of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fujian Institute of Research on the Structure of Matter of CAS filed Critical Fujian Institute of Research on the Structure of Matter of CAS
Priority to CN201210063660.5A priority Critical patent/CN102583583B/en
Publication of CN102583583A publication Critical patent/CN102583583A/en
Application granted granted Critical
Publication of CN102583583B publication Critical patent/CN102583583B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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 invention discloses a cathode material of manganese, cobalt and lithium oxidate for a lithium ion battery and a preparation method of the cathode material. The chemical formula of the cathode material is as follow: Li(3+x)/3Mn2x/1-xO2, wherein x is larger than or equal to 0.1 and is less than or equal to 0.9. The cathode material has excellent electrochemistry performances of high specific capacity, applicability of high temperature and low temperature, and the like. The preparation method is characterized by simplicity in operation, low manufacturing cost, short synthesis period, high repeatability and the like; no foreign ion is introduced, so that the purity of the product is greatly improved; lithium ions and transitional metal ions settle together, so that all the ions are mixed more uniformly; and the method can be extensively applied to synthesis of cathode material of oxidate for the lithium ion battery.

Description

A kind of lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof
Technical field
The present invention relates to a kind of manganese cobalt lithium oxide anode material in the lithium ion battery field and preparation method thereof, the chemical formula of this positive electrode material can be expressed as: Li (3+x)/3Mn 2x/3Co 1-xO 2, 0.1≤x≤0.9 wherein.
Background technology
Because lithium ion battery has high-voltage, heavy body, has extended cycle life, advantages such as safety performance is good, environmental protection, has been widely used in fields such as portable electric appts, PWR PLT, aerospace, space technology.Coprecipitation method is synthesized lithium ion battery transition metal oxide positive electrode material, and have great advantage: (1) product particle is uniformly dispersed, the particle size distribution homogeneous; (2) technological process is simple, is easy to control, is easy to scale operation; (3) production unit is required simply, production cost is low etc.Though prior coprecipitation method (is precipitation agent with NaOH) has many advantages, still exists very big weak point.Such as: (1) is preparation transition metal hydroxide precursor earlier, again with lithium salts blended technology, not only makes production complicated, and is unfavorable for the homogeneity of product; (2) in order to form transition metal hypostasis altogether, have under the condition of gas shield, add precipitation agent, make again that so production is complicated, has improved production cost, and has been unfavorable for scale operation; (3) different supersaturation property causes presoma phase composite fluctuation between the transition metal hydroxide, makes the coprecipitation process poor repeatability; (4) be that precipitation agent has inevitably been introduced foreign ion---Na with NaOH +, improved the water-absorbent of product, the chemical property of positive electrode material is worsened.Yet, the method that the present invention adopts, the above-mentioned deficiency that perfectly solves has further been simplified production technique, has improved performance of products.Adopt the material of the inventive method preparation, excellent product performance, technological process is simple, is easy to control, good reproducibility, cost is low, has the heavy industrialization application prospect.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof, the chemical formula of this positive electrode material can be expressed as: Li (3+x)/3Mn 2x/3Co 1-xO 2, 0.1≤x≤0.9 wherein.
Li provided by the present invention (3+x)/3Mn 2x/3Co 1-xO 2Positive electrode material is as the positive electrode material of lithium ion battery, not only has excellent electrochemical properties during room temperature, and also has excellent electrochemical properties under the high/low temperature condition.
Li provided by the invention (3+x)/3Mn 2x/3Co 1-xO 2The preparation method of positive electrode material may further comprise the steps:
(1) at first take by weighing lithium salts, manganese salt and cobalt salt, the ratio that makes metals ion Li: Mn: Co is 1.033: 0.067: 0.9～1.3: 0.6: 0.1, and the metal-salt that takes by weighing is dissolved in absolute ethyl alcohol, obtains ethanolic soln;
(2) take by weighing the oxalic acid that is in excess in stoichiometric ratio slightly, and be dissolved in the absolute ethyl alcohol, and add in the ethanolic soln that step (1) obtains, stir back suction filtration and dry, obtain (LiMnCo) xC 2O 4Presoma;
(3) (LiMnCo) that step (2) is obtained xC 2O 4Presoma heat-treat with processing under cooling after, obtain Li (3+x)/3Mn 2x/3Co 1-xO 2The positive electrode material powder.
Lithium salts in the above-mentioned steps (1) is one or more in lithium acetate, lithium nitrate, the lithium chloride; Manganese salt is one or more in manganous acetate, manganous nitrate, the Manganous chloride tetrahydrate; Cobalt salt is one or more in cobaltous acetate, Xiao Suangu, the NSC 51149;
The presoma of step (2) gained is the common hypostasis of lithium ion and transition metal ion, and churning time is 0.5h～2h;
Thermal treatment temp is 800 ℃～1000 ℃ in the step (3), time 3～16h; The processing under cooling mode is to quench in quenching, the mixture of ice and water in quenching, the liquid nitrogen under the room temperature.
The present invention adopts coprecipitation method to prepare Li (3+x)/3Mn 2x/3Co 1-xO 2Positive electrode material; With the absolute ethyl alcohol is solvent, and oxalic acid is precipitation agent, makes lithium ion and transition metal ion form common hypostasis; Solved lithium ion in the coprecipitation method in the past and failed to form the problem of common hypostasis, improved the degree that is uniformly dispersed and the homogeneity of product greatly with transition metal ion; The method that the present invention adopts is not introduced foreign ion, has improved product gas purity to a great extent, has solved the problem that foreign ion works the mischief to material property; In addition, the method that the present invention takes has shortened process step greatly, has practiced thrift ample resources, helps sequencing production, has practiced thrift production cost.The raw material sources that the present invention adopts are extensive, and process engineering is simple, are easy to control, and good reproducibility can synthesize in mass-producing.The compound method that the present invention adopts is not limited to the material that the present invention announces, can also be used for the synthetic of other materials, and this method has broad application prospects.
Description of drawings
Fig. 1 is embodiment 1Li 1.2Mn 0.4Co 0.4O 2The X-ray diffracting spectrum of positive electrode material powder.
Fig. 2 is embodiment 1Li 1.2Mn 0.4Co 0.4O 2The SEM figure of positive electrode material powder.
Fig. 3 uses Li for embodiment 1 1.2Mn 0.4Co 0.4O 2The positive electrode material powder is as positive pole 20mAg at room temperature -1, 60mAg -1, 100mAg -1, 200mAg -1The time charging and discharging curve.
Fig. 4 uses Li for embodiment 1 1.2Mn 0.4Co 0.4O 2The positive electrode material powder is as positive pole 20mAg at room temperature -1, 60mAg -1, 100mAg -1, 200mAg -1The time the cycle performance curve.
Embodiment
Main implementation process of the present invention is:
(1) at first take by weighing a certain amount of lithium salts, manganese salt and cobalt salt, the ratio that makes metals ion Li:Mn:Co is 1.033: 0.067: 0.9～1.3: 0.6: 0.1, and the metal-salt that takes by weighing is dissolved in absolute ethyl alcohol, obtains ethanolic soln;
(2) take by weighing the oxalic acid that is in excess in stoichiometric ratio slightly, and be dissolved in the absolute ethyl alcohol, and add in the ethanolic soln that obtains in the step (1), suction filtration and dry obtains (LiMnCo) behind the stirring certain hour xC 2O 4Presoma;
(3) (LiMnCo) that step (2) is obtained xC 2O 4After presoma is heat-treated and carried out processing under cooling, obtain Li (3+x)/3Mn 2x/3Co 1-xO 2The positive electrode material powder.
Below further illustrate characteristics of the present invention through instance, but be not limited to embodiment.
Experimental technique among the following embodiment if no special instructions, is ordinary method.
Embodiment 1:Li 1.2Mn 0.4Co 0.4O 2Positive electrode material
With lithium acetate, manganous acetate, cobaltous acetate and oxalic acid are starting raw material, and 0.9804g manganous acetate, 0.9964g cobaltous acetate, 1.2855g lithium acetate are dissolved in absolute ethyl alcohol, get the alcoholic acid metal salt solution; To be dissolved in absolute ethyl alcohol than the oxalic acid 2.1634g of stoichiometric ratio excessive 20% again; The ethanolic soln of oxalic acid is added in the alcoholic acid metal salt solution, stir behind the 1h suction filtration and behind 100 ℃ of dry 3h, be ground into the powder crucible of packing into; Heat-up rate with 4 ℃/min in box-type furnace is warmed up to 900 ℃ of heating 12h down, and under room temperature, anneals, and can obtain Li 1.2Mn 0.4Co 0.4O 2Powder body material.The XRD test result of powder body material shows that the synthetic powder has stratiform rock salt structure (R3m), and is as shown in Figure 1.The SEM test result of powder body material shows that the synthetic powder granule is evenly distributed, and size is 300～500nm, and is as shown in Figure 2.Adopt button cell to test, the mass ratio of mixed powder, conductive carbon black and sticker PVDF (pvdf) is 8: 1: 1, and metal lithium sheet is to the utmost point, 1molL -1LiPF 6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolytic solution, and polypropylene material is a barrier film, and battery test system is NEWARE TC53, and the charging/discharging voltage window is 2.0～4.6V, and charging and discharging currents density is chosen 20mAg respectively -1, 60mAg -1, 100mAg -1, 200mAg -1, this material shows good electrochemical during as lithium ion battery anodal.The button cell test result shows that (1) is at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and 28 ℃ of following first discharge specific capacity be respectively 270mAhg -1, 250mAhg -1, 238mAhg -1, 202mAhg -1, as shown in Figure 3; After discharging and recharging through 28 times, their specific discharge capacity is respectively 224mAhg -1, 198mAhg -1, 173mAhg -1, 164mAhg -1, as shown in Figure 4.(2) at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and-10 ℃ of following first discharge specific capacity be respectively 189mAhg -1, 162mAhg -1, 141mAhg -1, 123mAhg -1, after discharging and recharging through 28 times, their specific discharge capacity is respectively 175mAhg -1, 152mAhg -1, 129mAhg -1, 117mAhg -1(3) at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and 45.4 ℃ of following first discharge specific capacity be respectively 293mAhg -1, 250mAhg -1, 248mAhg -1, 211mAhg -1After discharging and recharging through 28 times, their specific discharge capacity is respectively 235mAhg -1, 198mAhg -1, 199mAhg -1, 159mAhg -1
Embodiment 2:Li 1.033Mn 0.067Co 0.9O 2Positive electrode material
With lithium acetate, manganous acetate, cobaltous acetate and oxalic acid are starting raw material, and 0.3270g manganous acetate, 4.4836g cobaltous acetate, 2.5305g lithium acetate are dissolved in absolute ethyl alcohol, get the alcoholic acid metal salt solution; To be dissolved in absolute ethyl alcohol than the oxalic acid 4.8021g of stoichiometric ratio excessive 20% again; The ethanolic soln of oxalic acid is added in the alcoholic acid metal salt solution, stir behind the 1h suction filtration and behind 100 ℃ of dry 3h, be ground into the powder crucible of packing into; Heat-up rate with 4 ℃/min in box-type furnace is warmed up to 900 ℃ of heating 12h down, and under room temperature, anneals, and can obtain Li 1.033Mn 0.067Co 0.9O 2Powder body material.The XRD test result of powder body material shows that the synthetic powder has stratiform rock salt structure (R3m).The SEM test result of powder body material shows that the synthetic powder granule is evenly distributed, and size is 300～500nm.Adopt button cell to test, the mass ratio of mixed powder, conductive carbon black and sticker PVDF (pvdf) is 8: 1: 1, and metal lithium sheet is to the utmost point, 1molL -1LiPF 6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolytic solution, and polypropylene material is a barrier film, and battery test system is NEWARE TC53, and the charging/discharging voltage window is 2.0～4.6V, and charging and discharging currents density is chosen 20mAg respectively -1, 60mAg -1, 100mAg -1, 200mAg -1, this material shows good electrochemical during as lithium ion battery anodal.The button cell test result shows that (1) is at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and 28 ℃ of following first discharge specific capacity be respectively 205mAhg -1, 185mAhg -1, 166mAhg -1, 143mAhg -1After discharging and recharging through 28 times, their specific discharge capacity is respectively 186mAhg -1, 162mAhg -1, 149mAhg -1, 131mAhg -1(2) at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and-10 ℃ of following first discharge specific capacity be respectively 173mAhg -1, 155mAhg -1, 136mAhg -1, 121mAhg -1, after discharging and recharging through 28 times, their specific discharge capacity is respectively 165mAhg -1, 146mAhg -1, 127mAhg -1, 114mAhg -1(3) at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and 45.4 ℃ of following first discharge specific capacity be respectively 236mAhg -1, 212mAhg -1, 196mAhg -1, 178mAhg -1After discharging and recharging through 28 times, their specific discharge capacity is respectively 204mAhg -1, 188mAhg -1, 172mAhg -1, 152mAhg -1
Embodiment 3:Li 1.1Mn 0.2Co 0.7O 2Positive electrode material
With lithium acetate, manganous acetate, cobaltous acetate and oxalic acid are starting raw material, and 0.9804g manganous acetate, 3.4873g cobaltous acetate, 2.4689g lithium acetate are dissolved in absolute ethyl alcohol, get the alcoholic acid metal salt solution; To be dissolved in absolute ethyl alcohol than the oxalic acid 6.3842g of stoichiometric ratio excessive 20% again; The ethanolic soln of oxalic acid is added in the alcoholic acid metal salt solution, stir behind the 1h suction filtration and behind 100 ℃ of dry 3h, be ground into the powder crucible of packing into; Heat-up rate with 4 ℃/min in box-type furnace is warmed up to 900 ℃ of heating 12h down, and under room temperature, anneals, and can obtain Li 1.1Mn 0.2Co 0.7O 2Powder body material.The XRD test result of powder body material shows that the synthetic powder has stratiform rock salt structure (R3m).The SEM test result of powder body material shows that the synthetic powder granule is evenly distributed, and size is 300～500nm.Adopt button cell to test, the mass ratio of mixed powder, conductive carbon black and sticker PVDF (pvdf) is 8: 1: 1, and metal lithium sheet is to the utmost point, 1molL -1LiPF 6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolytic solution, and polypropylene material is a barrier film, and battery test system is NEWARE TC53, and the charging/discharging voltage window is 2.0～4.6V, and charging and discharging currents density is chosen 20mAg respectively -1, 60mAg -1, 100mAg -1, 200mAg -1, this material shows good electrochemical during as lithium ion battery anodal.The button cell test result shows that (1) is at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and 28 ℃ of following first discharge specific capacity be respectively 219mAhg -1, 206mAhg -1, 187mAhg -1, 168mAhg -1After discharging and recharging through 28 times, their specific discharge capacity is respectively 188mAhg -1, 177mAhg -1, 164mAhg -1, 147mAhg -1(2) at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and-10 ℃ of following first discharge specific capacity be respectively 176mAhg -1, 159mAhg -1, 142mAhg -1, 118mAhg -1, after discharging and recharging through 28 times, their specific discharge capacity is respectively 168mAhg -1, 149mAhg -1, 131mAhg -1, 112mAhg -1(3) at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and 45.4 ℃ of following first discharge specific capacity be respectively 240mAhg -1, 226mAhg -1, 201mAhg -1, 186mAhg -1After discharging and recharging through 28 times, their specific discharge capacity is respectively 206mAhg -1, 194mAhg -1, 176mAhg -1, 165mAhg -1
Embodiment 4:Li 1.15Mn 0.3Co 0.55O 2Positive electrode material
With lithium acetate, manganous acetate, cobaltous acetate and oxalic acid are starting raw material, and 1.4705g manganous acetate, 2.7400g cobaltous acetate, 2.5811g lithium acetate are dissolved in absolute ethyl alcohol, get the alcoholic acid metal salt solution; To be dissolved in absolute ethyl alcohol than the oxalic acid 6.3993g of stoichiometric ratio excessive 20% again; The ethanolic soln of oxalic acid is added in the alcoholic acid metal salt solution, stir behind the 1h suction filtration and behind 100 ℃ of dry 3h, be ground into the powder crucible of packing into; Heat-up rate with 4 ℃/min in box-type furnace is warmed up to 900 ℃ of heating 12h down, and under room temperature, anneals, and can obtain Li 1.15Mn 0.3Co 0.55O 2Powder body material.The XRD test result of powder body material shows that the synthetic powder has stratiform rock salt structure (R3m).The SEM test result of powder body material shows that the synthetic powder granule is evenly distributed, and size is 300～500nm.Adopt button cell to test, the mass ratio of mixed powder, conductive carbon black and sticker PVDF (pvdf) is 8: 1: 1, and metal lithium sheet is to the utmost point, 1molL -1LiPF 6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolytic solution, and polypropylene material is a barrier film, and battery test system is NEWARE TC53, and the charging/discharging voltage window is 2.0～4.6V, and charging and discharging currents density is chosen 20mAg respectively -1, 60mAg -1, 100mAg -1, 200mAg -1, this material shows good electrochemical during as lithium ion battery anodal.The button cell test result shows that (1) is at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and 28 ℃ of following first discharge specific capacity be respectively 248mAhg -1, 229mAhg -1, 206mAhg -1, 188mAhg -1After discharging and recharging through 28 times, their specific discharge capacity is respectively 215mAhg -1, 198mAhg -1, 181mAhg -1, 165mAhg -1(2) at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and-10 ℃ of following first discharge specific capacity be respectively 170mAhg -1, 153mAhg -1, 139mAhg -1, 119mAhg -1, after discharging and recharging through 28 times, their specific discharge capacity is respectively 162mAhg -1, 143mAhg -1, 128mAhg -1, 108mAhg -1(3) at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and 45.4 ℃ of following first discharge specific capacity be respectively 268mAhg -1, 244mAhg -1, 217mAhg -1, 191mAhg -1After discharging and recharging through 28 times, their specific discharge capacity is respectively 235mAhg -1, 212mAhg -1, 193mAhg -1, 170mAhg -1
Embodiment 5:Li 1.3Mn 0.6Co 0.1O 2Positive electrode material
With lithium acetate, manganous acetate, cobaltous acetate and oxalic acid are starting raw material, and 2.9411g manganous acetate, 0.4982g cobaltous acetate, 2.7851g lithium acetate are dissolved in absolute ethyl alcohol, get the alcoholic acid metal salt solution; To be dissolved in absolute ethyl alcohol than the oxalic acid 4.1830g of stoichiometric ratio excessive 20% again; The ethanolic soln of oxalic acid is added in the alcoholic acid metal salt solution, stir behind the 1h suction filtration and behind 100 ℃ of dry 3h, be ground into the powder crucible of packing into; Heat-up rate with 4 ℃/min in box-type furnace is warmed up to 900 ℃ of heating 12h down, and under room temperature, anneals, and can obtain Li 1.3Mn 0.6Co 0.1O 2Powder body material.The XRD test result of powder body material shows that the synthetic powder has stratiform rock salt structure (R3m).The SEM test result of powder body material shows that the synthetic powder granule is evenly distributed, and size is 300～500nm.Adopt button cell to test, the mass ratio of mixed powder, conductive carbon black and sticker PVDF (pvdf) is 8: 1: 1, and metal lithium sheet is to the utmost point, 1molL -1LiPF 6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolytic solution, and polypropylene material is a barrier film, and battery test system is NEWARE TC53, and the charging/discharging voltage window is 2.0～4.6V, and charging and discharging currents density is chosen 20mAg respectively -1, 60mAg -1, 100mAg -1, 200mAg -1, this material shows good electrochemical during as lithium ion battery anodal.The button cell test result shows that (1) is at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and 28 ℃ of following first discharge specific capacity be respectively 192mAhg -1, 173mAhg -1, 155mAhg -1, 129mAhg -1After discharging and recharging through 28 times, their specific discharge capacity is respectively 164mAhg -1, 148mAhg -1, 140mAhg -1, 117mAhg -1(2) at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and-10 ℃ of following first discharge specific capacity be respectively 121mAhg -1, 107mAhg -1, 96mAhg -1, 83mAhg -1, after discharging and recharging through 28 times, their specific discharge capacity is respectively 113mAhg -1, 99mAhg -1, 86mAhg -1, 79mAhg -1(3) at 20mAg -1, 60mAg -1, 100mAg -1, 200mAg -1Charging and discharging currents density and 45.4 ℃ of following first discharge specific capacity be respectively 208mAhg -1, 185mAhg -1, 174mAhg -1, 153mAhg -1After discharging and recharging through 28 times, their specific discharge capacity is respectively 181mAhg -1, 166mAhg -1, 154mAhg -1, 137mAhg -1

Claims (5)

1. lithium ion battery manganese cobalt lithium oxide anode material, it is characterized in that: the chemical formula of this material can be: Li (3+x)/3Mn 2x/3Co 1-xO 2, 0.1≤x≤0.9 wherein.
2. the preparation method of the described lithium ion battery manganese of claim 1 a cobalt lithium oxide anode material comprises the steps:
(1) at first take by weighing lithium salts, manganese salt and cobalt salt, the ratio that makes metals ion Li: Mn: Co is 1.033: 0.067: 0.9～1.3: 0.6: 0.1, and the metal-salt that takes by weighing is dissolved in absolute ethyl alcohol, obtains ethanolic soln;
(2) take by weighing the oxalic acid that is in excess in stoichiometric ratio slightly, and be dissolved in the absolute ethyl alcohol, and add in the ethanolic soln that step (1) obtains, stir back suction filtration and dry, obtain (LiMnCo) xC 2O 4Presoma;
(3) (LiMnCo) that step (2) is obtained xC 2O 4Presoma heat-treat with processing under cooling after, obtain Li (3+x)/3Mn 2x/3Co 1-xO 2The positive electrode material powder.
3. the preparation method of lithium ion battery manganese cobalt lithium oxide anode material according to claim 2, it is characterized in that: described lithium salts is one or more in lithium acetate, lithium nitrate, the lithium chloride; Described manganese salt is one or more in manganous acetate, manganous nitrate, the Manganous chloride tetrahydrate; Described cobalt salt is one or more in cobaltous acetate, Xiao Suangu, the NSC 51149.
4. the preparation method of lithium ion battery manganese cobalt lithium oxide anode material according to claim 2 is characterized in that: described presoma is that the oxalate of lithium ion and transition metal ion is total to hypostasis, and churning time is 0.5h～2h.
5. the preparation method of lithium ion battery manganese cobalt lithium oxide anode material according to claim 2 is characterized in that: thermal treatment temp is 800 ℃～1000 ℃ in the said step (3), time 3～16h; The processing under cooling mode is to quench in quenching, the mixture of ice and water in quenching, the liquid nitrogen under the room temperature.
CN201210063660.5A 2012-03-12 2012-03-12 A kind of lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof Active CN102583583B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210063660.5A CN102583583B (en) 2012-03-12 2012-03-12 A kind of lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210063660.5A CN102583583B (en) 2012-03-12 2012-03-12 A kind of lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102583583A true CN102583583A (en) 2012-07-18
CN102583583B CN102583583B (en) 2016-06-29

Family

ID=46472946

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210063660.5A Active CN102583583B (en) 2012-03-12 2012-03-12 A kind of lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102583583B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102903909A (en) * 2012-10-22 2013-01-30 中国科学院福建物质结构研究所 Manganese-cobalt-lithium oxide positive electrode material of lithium ion battery and preparation method of material
CN103715411A (en) * 2013-12-17 2014-04-09 中国科学院福建物质结构研究所 Lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof
CN104201328A (en) * 2014-08-22 2014-12-10 东莞市迈科科技有限公司 High-capacity lithium anode material and preparation method thereof
CN104201373A (en) * 2014-08-22 2014-12-10 东莞市迈科科技有限公司 Lithium-rich anode material and preparation method thereof
CN104409685A (en) * 2014-11-28 2015-03-11 东莞市迈科科技有限公司 Lithium ion cell cathode material with core shell structure and preparation method thereof
CN105958052A (en) * 2016-05-29 2016-09-21 合肥国轩高科动力能源有限公司 Preparation method for metal-element-doped manganese-based positive electrode material for lithium ion battery
CN106252650A (en) * 2016-10-31 2016-12-21 安徽工业大学 A kind of preparation method of stratiform lithium-rich manganese-based anode material
CN107768639A (en) * 2017-10-19 2018-03-06 深圳市比克动力电池有限公司 Anode material of lithium battery and preparation method thereof, the lithium battery using the positive electrode

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DONGQIANG LIU ET AL.: "Structure, morphology, and cathode performance of Li1−x[Ni0.5Mn1.5]O4prepared by coprecipitation with oxalic acid", 《JOURNAL OF POWER SOURCES》 *
DONGQIANG LIU ET AL.: "Structure, morphology, and cathode performance of Li1−x[Ni0.5Mn1.5]O4prepared by coprecipitation with oxalic acid", 《JOURNAL OF POWER SOURCES》, 13 November 2009 (2009-11-13), pages 2918 - 2923 *
Y.J. WEI ET AL.: "Electrochemical kinetics and cycling performance of nano Li[Li0.23Co0.3Mn0.47]O2 cathode material for lithium ion batteries", 《ELECTROCHEMISTRY COMMUNICATIONS》 *
ZHE LI ET AL.: "Low temperature properties of the Li[Li0.2Co0.4Mn0.4]O2 cathode material for Li-ion batteries", 《ELECTROCHEMISTRY COMMUNICATIONS》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102903909A (en) * 2012-10-22 2013-01-30 中国科学院福建物质结构研究所 Manganese-cobalt-lithium oxide positive electrode material of lithium ion battery and preparation method of material
CN103715411A (en) * 2013-12-17 2014-04-09 中国科学院福建物质结构研究所 Lithium ion battery manganese cobalt lithium oxide anode material and preparation method thereof
CN104201328A (en) * 2014-08-22 2014-12-10 东莞市迈科科技有限公司 High-capacity lithium anode material and preparation method thereof
CN104201373A (en) * 2014-08-22 2014-12-10 东莞市迈科科技有限公司 Lithium-rich anode material and preparation method thereof
CN104409685A (en) * 2014-11-28 2015-03-11 东莞市迈科科技有限公司 Lithium ion cell cathode material with core shell structure and preparation method thereof
CN104409685B (en) * 2014-11-28 2017-09-22 东莞市迈科科技有限公司 A kind of method for preparing the anode material for lithium-ion batteries with core shell structure
CN105958052A (en) * 2016-05-29 2016-09-21 合肥国轩高科动力能源有限公司 Preparation method for metal-element-doped manganese-based positive electrode material for lithium ion battery
CN106252650A (en) * 2016-10-31 2016-12-21 安徽工业大学 A kind of preparation method of stratiform lithium-rich manganese-based anode material
CN106252650B (en) * 2016-10-31 2018-11-13 安徽工业大学 A kind of preparation method of stratiform lithium-rich manganese-based anode material
CN107768639A (en) * 2017-10-19 2018-03-06 深圳市比克动力电池有限公司 Anode material of lithium battery and preparation method thereof, the lithium battery using the positive electrode

Also Published As

Publication number Publication date
CN102583583B (en) 2016-06-29

Similar Documents

Publication Publication Date Title
CN102244257B (en) High-temperature manganic acid lithium cathode material and preparation method thereof
CN102583583A (en) Cathode material of manganese, cobalt and lithium oxidate for lithium ion battery and preparation method of cathode material
KR101198489B1 (en) A method for preparing iron source used for preparing lithium ferrous phosphate, and a method for preparing lithium ferrous phosphate
CN102683669B (en) Anode material for lithium-ion batteries and preparation method thereof
CN103794773B (en) A kind of method of producing high power capacity 523 type tertiary cathode material
CN108767239A (en) A kind of nickelic low cobalt tertiary cathode material and preparation method thereof
CN101800315A (en) Multielement-doped lithium iron phosphate positive electrode material and preparation method thereof
CN103840148A (en) Method for preparation of multi-element composite lithium ion battery anode material by secondary sintering
CN102694164B (en) Lithium oxide-rich cathode material with nitrogen or carbon-doped surface and preparation method for cathode material
CN102751481A (en) Li2MnO3 and LiCoO2 composite anode material
CN104466099A (en) High-voltage lithium cobaltate based composite cathode material of lithium ion battery and preparation method of high-voltage lithium cobaltate based composite cathode material
CN103078113A (en) Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof
CN101327921B (en) Preparation of ferric phosphate lithium composite material
CN105720254A (en) Preparation method for carbon-coated lithium vanadate used as negative electrode material of lithium ion battery
Huang et al. High rate and thermally stable Mn-rich concentration-gradient layered oxide microsphere cathodes for lithium-ion batteries
CN100490221C (en) Composite doped modified lithium-ion battery anode material and its manufacture method
CN102751483A (en) Layered rich-lithium-manganese-based solid-solution anode material of lithium ion battery and method for preparing anode material
Gu et al. Synthesis of spinel LiNixMn2-xO4 (x= 0, 0.1, 0.16) and their high rate charge-discharge performances
CN103187566B (en) Tubular lithium-rich anode material, preparation method and application thereof
CN108110242A (en) A kind of preparation method of lithium ion battery nickel manganese cobalt composite material
CN105161712A (en) Nickel lithium manganate cathode material and preparation method and application thereof
CN102593443A (en) Method for preparing cathode activated nanometer composite material
Liu et al. Uniformly sodium ions doped LiNi0. 84Co0. 11Mn0. 05O2 cathode material with high performance for lithium-ion batteries
CN103456945A (en) Preparation method of low-cost lithium ion battery anode material
CN101456581A (en) Method for preparing lithium ion secondary battery cathode material lithium titanate containing rare-earth element

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant