CN103050685A - Preparation method for improving positive electrode material LiCoO2 electrical performance - Google Patents
Preparation method for improving positive electrode material LiCoO2 electrical performance Download PDFInfo
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- CN103050685A CN103050685A CN2012103580688A CN201210358068A CN103050685A CN 103050685 A CN103050685 A CN 103050685A CN 2012103580688 A CN2012103580688 A CN 2012103580688A CN 201210358068 A CN201210358068 A CN 201210358068A CN 103050685 A CN103050685 A CN 103050685A
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Abstract
The invention discloses a preparation method for improving the positive electrode material LiCoO2 electrical performance. The preparation method for improving the positive electrode material LiCoO2 electrical performance is completed according to the following steps of: mixing cobaltosic oxide and lithium salt (adding an additive T1); pretreating; sintering for the first time at the temperature of 600-11000 DEG C for 6-20 hours; carrying out surface treatment; mixing for the second time; pretreating; sintering in an inert atmosphere at 400-800 DEG C for 5-10 hours, and sintering for the second time at low temperature; and carrying out surface treatment, thereby obtaining the product. Modified lithium cobalt oxides prepared by the method provided by the invention not only have the original properties, but also can achieve high-magnification high-current charge and discharge; a battery prepared from lithium sheets as negative electrode materials tests, the test current magnification is 0.2C, and the voltage range is 2.9V-4.2V; the specific capacity of the tested material is greater than 160mAh/g in circulation for 100 times; the discharge platform retention rate is above 85%; and the capacity retention rate is above 95%.
Description
Technical field
The present invention relates to the preparation method of a kind of lithium ion cell anode material lithium cobaltate conductivity modification, belong to the technical field of new forms of energy and energy-efficient-new and effective energy conversion and storing technology and Related product preparation.
Background technology
Cobalt acid lithium is the positive electrode of lithium ion battery, also be the key components of lithium ion battery, account for about 1/3rd of lithium ion battery cell material cost, be that present production technology is the most ripe, battery performance is the most reliable and obtain the anode material for lithium-ion batteries of broad commercial applications.Cobalt acid lithium is widely used in the small-sized movable electronic product batteries such as mobile phone, portable computer, video camera as the positive electrode of lithium ion battery main flow, and generally these fields all belong to low discharging current.Now, height progress along with space technology and military science and technology, electronic message unit is day by day to lightweight, miniaturization and portable future development, for some heavy-current discharge fields (namely high-multiplying power discharge), the commercially available prod conductive capability is relatively poor at present, capacity is low, can not realize high power charging-discharging.
Summary of the invention:
Purpose of the present invention just is to overcome above-mentioned the deficiencies in the prior art, and a kind of positive electrode LiCoO that improves is provided
2The preparation method of electrical property utilizes that this preparation method can obtain that high power charging-discharging, conductive capability are strong, the lithium cobaltate cathode material of high power capacity, security performance and superior electrical property.
As above design, technical scheme of the present invention is: a kind of positive electrode LiCoO that improves
2The preparation method of electrical property is characterized in that: finish according to the following step:
1) selecting the lithium carbonate of LITHIUM BATTERY or the cobaltosic oxide of lithium hydroxide and LITHIUM BATTERY is raw material, and carries out proportioning according to the ratio of lithium cobalt mol ratio 1 ~ 1.1:1; Select Bi, Sn, Ce, Ti, Mo, Zr, V, Cr, the Nb of rare earth oxide, higher valence state, in the Ni transition metal oxide one or more as additive T1, the weight of every kind of additive is 0.05% ~ 0.2% of cobaltosic oxide weight; Cobaltosic oxide and the additive T1 of the lithium carbonate of LITHIUM BATTERY or lithium hydroxide, LITHIUM BATTERY are mixed;
2) with 1) material that obtains mixing sintering 6 ~ 20 hours under 600 ~ 1100 ℃ of temperature, and through surface treatment, obtain highdensity cobalt acid lithium one defective material;
3) 2) in add carbonaceous material in cobalt acid lithium one defective material that obtains and mix, the carbon content weight ratio is 0.02% ~ 5% of cobalt acid lithium one defective material weight, according to carbometer calculate add the weight of carbonaceous material;
4) with 3) material that mixes sintering 5 ~ 10 hours in 400 ~ 800 ℃ of inert atmospheres, and insulation 8-10 hour under 300 ~ 800 ℃ of temperature, at last these materials are pulverized, sieved, can obtain carbon modified parcel lithium cobaltate cathode material.
Above-mentioned additive T1 selects TiO
2, Al
2O
3, Nd
2O
3, Nb
2O
5In the rare earth oxide one or more.
Above-mentioned carbon containing carbonaceous material is selected one or more in sucrose, citric acid, glucose, the nano-carbon powder.
The present invention adopts the treatment process of double sintering: once sintered Bi, Sn, Ce, Ti, Mo, Zr, V, Cr, the transition metal oxides such as Nb, Ni of sneaking into rare earth oxide, higher valence state, utilize the characteristic of these elements when high temperature, form structural integrity, high compacted density, the superior modification compound lithium cobaltate of cycle performance; In the modification compound lithium cobaltate, add again carbonaceous material under inert gas shielding, be warmed to uniform temperature and carry out the sintering second time, make its carbonization, be coated on uniformly cobalt acid crystalline lithium surface.
The modified cobalt acid lithium that utilizes the present invention to produce not only has original character, but also can realize high magnification, high current charge-discharge.The battery of making take the lithium sheet as negative material is tested, and the measuring current multiplying power is 0.2C, and voltage range is between 2.9V ~ 4.2V, record the specific capacity of material greater than 160mAh/g, circulate 100 times, the discharge platform conservation rate is more than 85%, and capability retention is more than 95%.
The product that utilizes the present invention to produce has following features:
1, the particle that monocrystalline is larger, higher compacted density, utmost point low specific surface area;
2, degree of crystallinity is high, drawing abillity is excellent;
3, chemical property is excellent, capacity is high, capability retention is high;
4, superior high-rate charge-discharge capability.
Description of drawings:
Fig. 1 is the XRD spectra of modification carbon coating cobalt acid lithium;
Fig. 2 is the SEM figure of modification carbon coating cobalt acid lithium;
Fig. 3 is the energy spectrogram of modification carbon coating cobalt acid lithium.
Embodiment:
Embodiment 1: a kind of positive electrode LiCoO that improves
2The preparation method of electrical property is characterized in that: finish according to the following step:
1) selecting the battery-level lithium carbonate of the neat lithium industry in sky, Sichuan and the GB-100 model cobaltosic oxide of Ningbo KeBoTe cobalt-nickel Co., Ltd is raw material, and carries out proportioning according to the ratio of lithium cobalt mol ratio 1.035:1.Add TiO
2, ZrO
2And Nb
2O
5As additive T1, wherein TiO
2Interpolation weight be cobaltosic oxide weight 0.12%, ZrO
2Interpolation weight be cobaltosic oxide weight 0.1%, Nb
2O
5Interpolation weight be 0.15% of cobaltosic oxide weight.GB-100 model cobaltosic oxide, TiO with battery-level lithium carbonate, Ningbo KeBoTe cobalt-nickel Co., Ltd
2, ZrO
2And Nb
2O
5Mixing is mixed, and mixes.
2) with 1) material that obtains mixing packs in the fire resistant sagger, pushes in the high temperature pusher kiln, slowly releases kiln in insulation under 600 ~ 960 ℃ of temperature after 12 hours, obtains highdensity cobalt acid lithium one defective material.
3) 2) in cobalt acid lithium one defective material that obtains, add the glucose of cobalt acid lithium one defective material weight 6%, and mix.
4) material that mixes is packed in the fire resistant sagger, push 300 ~ 600 ℃ of N
2Insulation is after 8 hours in the high temperature kiln of Buchholz protection, slowly releases kiln after being cooled to room temperature.
5) material of coming out of the stove is pulverized, sieved, can obtain carbon modified of the present invention and coat lithium cobaltate cathode material.
Adopt the prepared carbon coating cobalt acid lithium of example 1 production technology, compacted density is 3.9 ~ 4.2g/cm3; The battery of making take the lithium sheet as negative material is tested, and the measuring current multiplying power is 0.2C, and voltage range is between 2.9V ~ 4.2V, and the specific capacity that records material is 160mAh/g, circulates 100 times the time, and the discharge platform conservation rate is 87%, and capability retention is 96%.
Embodiment 2: a kind of positive electrode LiCoO that improves
2The preparation method of electrical property is characterized in that: finish according to the following step:
1) selecting the battery-level lithium carbonate of the neat lithium industry in sky, Sichuan and the GB-100 model cobaltosic oxide of Ningbo KeBoTe cobalt-nickel Co., Ltd is raw material, and carries out proportioning according to the ratio of lithium cobalt mol ratio 1.045:1.Add TiO
2, CeO
2And Nb
2O
5As additive T1, wherein TiO
2Interpolation weight be cobaltosic oxide weight 0.12%, ZrO
2Interpolation weight be cobaltosic oxide weight 0.1%, Nb
2O
5Interpolation weight be 0.15% of cobaltosic oxide weight.GB-100 model cobaltosic oxide, TiO with battery-level lithium carbonate, Ningbo KeBoTe cobalt-nickel Co., Ltd
2, ZrO
2And Nb
2O
5Mixing is mixed, and mixes.
2) with 1) material that obtains mixing packs in the fire resistant sagger, pushes in the high temperature pusher kiln, slowly releases kiln in insulation under 600 ~ 1100 ℃ of temperature after 10 hours.
3) 2) in cobalt acid lithium one defective material that obtains, add the citric acid of cobalt acid lithium one defective material weight 8%, and mix.
4) material that mixes is packed in the fire resistant sagger, push 300 ~ 700 ℃ of N
2In the high temperature kiln of Buchholz protection, be incubated after 10 hours, be cooled to and slowly release kiln after the room temperature.
5) material of coming out of the stove is pulverized, sieved, can obtain carbon modified of the present invention and coat lithium cobaltate cathode material.
Adopt the prepared modification carbon coating cobalt acid lithium of embodiment 2 production technologies, compacted density is 3.9 ~ 4.2g/cm3; The battery of making take the lithium sheet as negative material is tested, and the measuring current multiplying power is 0.2C, and voltage range is between 2.9V ~ 4.2V, and the specific capacity that records material is 161.1mAh/g, circulates 100 times the time, and the discharge platform conservation rate is 87%, and capability retention is 95.5%.
In sum, the present invention takes charge of on the basis of original HYC-A type lithium ion cell anode material lithium cobaltate at me, utilization has the organic carbon material of superpower conductive capability, improve multiplying power, the cycle performance of cobalt acid lithium, thereby material is had using in the market outside the characteristics such as cobalt acid lithium high-energy, long circulation life, good processing characteristics, good security performance, high-quality specific energy, but also can realize large electric current, high-multiplying power discharge; The carbon coating cobalt acid lithium anode material compacted density of this law preparation can accomplish that between 3.9 ~ 4.2g/cm3, the electrochemical discharge capacity reaches more than the 160mAh/g, can satisfy the above heavy-current discharge of 5C.
Claims (3)
1. one kind is improved positive electrode LiCoO
2The preparation method of electrical property is characterized in that: finish according to the following step:
1) selecting the lithium carbonate of LITHIUM BATTERY or the cobaltosic oxide of lithium hydroxide and LITHIUM BATTERY is raw material, and carries out proportioning according to the ratio of lithium cobalt mol ratio 1 ~ 1.1:1; Select Bi, Sn, Ce, Ti, Mo, Zr, V, Cr, the Nb of rare earth oxide, higher valence state, in the Ni transition metal oxide one or more as additive T1, the weight of every kind of additive is 0.05% ~ 0.2% of cobaltosic oxide weight; Cobaltosic oxide and the additive T1 of the lithium carbonate of LITHIUM BATTERY or lithium hydroxide, LITHIUM BATTERY are mixed;
2) with 1) material that obtains mixing sintering 6 ~ 20 hours under 600 ~ 1100 ℃ of temperature, and through surface treatment, obtain highdensity cobalt acid lithium one defective material;
3) 2) in add carbonaceous material in cobalt acid lithium one defective material that obtains and mix, the carbon content weight ratio is 0.02% ~ 5% of cobalt acid lithium one defective material weight, according to carbometer calculate add the weight of carbonaceous material;
4) with 3) material that mixes sintering 5 ~ 10 hours in 400 ~ 800 ℃ of inert atmospheres, at last these materials are pulverized, sieved, can obtain carbon modified parcel lithium cobaltate cathode material.
2. a kind of positive electrode LiCoO that improves according to claim 1
2The preparation method of electrical property is characterized in that: above-mentioned additive T1 selects TiO
2, Al
2O
3, Nd
2O
3, Nb
2O
5In the rare earth oxide one or more.
3. a kind of positive electrode LiCoO that improves according to claim 1
2The preparation method of electrical property is characterized in that: above-mentioned carbon containing carbonaceous material is selected one or more in sucrose, citric acid, glucose, the nano-carbon powder.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103746114A (en) * | 2014-01-29 | 2014-04-23 | 厦门钨业股份有限公司 | Preparation method for lithium cobalt oxide anode material |
| CN103794785A (en) * | 2014-02-21 | 2014-05-14 | 刘洋 | Preparation method of lanthanum ferrum nickel doped lithium cobaltate-carbon composite positive electrode material |
| CN110563052A (en) * | 2019-09-09 | 2019-12-13 | 河北省科学院能源研究所 | preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102237515A (en) * | 2010-04-20 | 2011-11-09 | 深圳市比克电池有限公司 | Lithium ion battery, active cathode material and preparation methods thereof |
| CN102244232A (en) * | 2010-05-13 | 2011-11-16 | 天津华夏泓源实业有限公司 | Method for preparing composite lithium cobaltate anode material with high capacity and high compact density |
-
2012
- 2012-09-24 CN CN2012103580688A patent/CN103050685A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102237515A (en) * | 2010-04-20 | 2011-11-09 | 深圳市比克电池有限公司 | Lithium ion battery, active cathode material and preparation methods thereof |
| CN102244232A (en) * | 2010-05-13 | 2011-11-16 | 天津华夏泓源实业有限公司 | Method for preparing composite lithium cobaltate anode material with high capacity and high compact density |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103746114A (en) * | 2014-01-29 | 2014-04-23 | 厦门钨业股份有限公司 | Preparation method for lithium cobalt oxide anode material |
| CN103746114B (en) * | 2014-01-29 | 2016-11-16 | 厦门钨业股份有限公司 | A kind of preparation method of lithium cobaltate cathode material |
| CN103794785A (en) * | 2014-02-21 | 2014-05-14 | 刘洋 | Preparation method of lanthanum ferrum nickel doped lithium cobaltate-carbon composite positive electrode material |
| CN103794785B (en) * | 2014-02-21 | 2016-06-08 | 太原工业学院 | A kind of preparation method of lanthanum ferrum nickel cation doping acid lithium-carbon composite anode material |
| CN110563052A (en) * | 2019-09-09 | 2019-12-13 | 河北省科学院能源研究所 | preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material |
| CN110563052B (en) * | 2019-09-09 | 2021-11-05 | 河北省科学院能源研究所 | Preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material |
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Application publication date: 20130417 |