CN103943857B - A kind of lithium ion battery LiMnBO 3/ KB composite positive pole and preparation method thereof - Google Patents

A kind of lithium ion battery LiMnBO 3/ KB composite positive pole and preparation method thereof Download PDF

Info

Publication number
CN103943857B
CN103943857B CN201410195633.2A CN201410195633A CN103943857B CN 103943857 B CN103943857 B CN 103943857B CN 201410195633 A CN201410195633 A CN 201410195633A CN 103943857 B CN103943857 B CN 103943857B
Authority
CN
China
Prior art keywords
limnbo
positive pole
solution
preparation
composite positive
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.)
Expired - Fee Related
Application number
CN201410195633.2A
Other languages
Chinese (zh)
Other versions
CN103943857A (en
Inventor
唐安平
周智华
贺冬华
徐国荣
刘立华
令玉林
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.)
Hunan University of Science and Technology
Original Assignee
Hunan University of Science and Technology
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 Hunan University of Science and Technology filed Critical Hunan University of Science and Technology
Priority to CN201410195633.2A priority Critical patent/CN103943857B/en
Publication of CN103943857A publication Critical patent/CN103943857A/en
Application granted granted Critical
Publication of CN103943857B publication Critical patent/CN103943857B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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 kind of lithium ion battery LiMnBO 3/ KB composite material and preparation method thereof.The method comprises the steps: first by water-soluble for soluble manganese salt formation solution, then KB is joined in solution and flood, deposition reaction is carried out again in carbonate or oxalate solution, then lock out operation and the washings such as suction filtration, centrifugal or press filtration are carried out to suspension, after finally the Solid separate obtained being mixed with lithium source, boron source, at 500 ~ 800 DEG C, sinter 5 ~ 10h in an inert atmosphere, namely obtain LiMnBO 3/ KB composite material.This composite material has higher specific discharge capacity, excellent cyclical stability and high rate performance.LiMnBO 3/ KB composite material is under C/40, C/20, C/10, C/5 multiplying power, and first discharge specific capacity is respectively 127,114,112 and 98mAh/g.Under C/20, C/10 multiplying power, after circulation in 30 weeks, specific discharge capacity is respectively 114 and 94mAh/g.

Description

A kind of lithium ion battery LiMnBO 3/ KB composite positive pole and preparation method thereof
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, particularly a kind of LiMnBO 3/ Ketjen black (KetchenBlack is abbreviated as KB) composite positive pole and preparation method thereof.
Background technology
Along with becoming increasingly conspicuous and the high speed development of modern science and technology of energy and environment problem, good cycle, operating voltage are high, the lithium ion battery of environmental protection is as the reusable resource of one, progress into the visual field of people, become the focus that people pay close attention to, be developed to alleviate energy shortage and environmental issue, and be widely used in the driving of portable electric appts, energy storage device and electric motor car.And the development of lithium ion battery electrode material unbalanced, wherein the development of positive electrode relatively lags behind, and has become one of key factor that restriction lithium ion battery overall performance improves further.At present, with olivine-type LiFePO 4for the polyanionic compound of representative has good performance as anode material for lithium-ion batteries, thus cause the extensive concern of people.Up to the present, major part research focuses on by SO 4 2-, PO 4 3-or SiO 4 4-deng the chemical property of the positive electrode of polyanion composition.Recently, LiMBO 3(M=Mn, Fe, Co) borate has also attracted certain attentiveness as anode material for lithium-ion batteries.
With SO 4 2-, PO 4 3-or SiO 4 4-compare Deng polyanion, BO 3 3-advantage be the little (58.8gmol of molal weight -1).Therefore, LiMBO 3(M=Mn, Fe, Co) may have higher specific capacity, such as LiFeBO 3, LiMnBO 3, LiCoBO 3theoretical specific capacity be respectively 220,222,215mAhg -1, compare LiFePO 4about exceed 50mAhg -1.This shows LiMBO 3likely develop into the lithium ion battery novel anode material of height ratio capacity.Add the advantage of its thermal stability and security performance aspect, there is huge application prospect in lithium-ion-power cell.Especially LiFeBO 3, its electronic conductivity compares LiFePO 4higher.Therefore, although LiMBO 3average voltage 0.4V lower than corresponding phosphate cathode material, but due to its theoretical specific capacity 50mAhg about higher than corresponding phosphate material -1, theoretical energy density still exceeds 10% than corresponding phosphate material.These advantages make LiMBO 3anode material for lithium-ion batteries as a new generation progressively enters the visual field of researcher.
In the iron reported at present, manganese, cobalt three kinds of borate positive electrodes, LiFeBO 3discharge voltage minimum, first-principles calculations result is 3.02V, and the discharge voltage of the latter two is relatively high, and first-principles calculations result is followed successively by 3.67 and 4.09V.Due to LiFeBO 3, LiMnBO 3and LiCoBO 3theoretical specific capacity be more or less the same, all at 220mAhg -1left and right, therefore, with LiFeBO 3compare, LiMnBO 3and LiCoBO 3there is higher theoretical energy density.In addition, compared with the strategic scarcity metals element such as cobalt, nickel, the advantage of manganese is aboundresources, cheap, nontoxic and environmentally friendly, and especially manganese is China's Dominant Mineral Resources, and explored promoter manganese reserves occupy third place in the world, account for 5% of global gross reserves; Moreover China is a Ge Peng resource big country, and proved reserves account for 16% of world's boron rock reserves.Therefore, in view of the composite factor of discharge voltage, theoretical energy density, cost of material and resources advantage, LiMnBO 3the research and development of positive electrode have positive effect to the utilization of China's manganese, boron resource and the development of the national economy.
Although LiFeBO 3, LiMnBO 3, LiCoBO 3be synthesized Deng borate compound, but be also in the starting stage about this kind of material as the research of anode material for lithium-ion batteries.Especially LiMnBO 3positive electrode, not only first discharge specific capacity is far away still lower than the theoretical specific capacity of its 222mAh/g, and its cycle performance is also very undesirable.So synthesis possesses the LiMnBO of high reversible specific capacity, long circulation life (such as cycle-index is greater than 200 times), excellent high rate performance simultaneously 3so far there is not been reported, how to synthesize the LiMnBO of electrochemical performance 3material is still a difficult problem of material and chemist facing.
Constant current (C/100 multiplying power) Intermittent Titration Technique result of study shows that kinetic factor is LiFeBO 3the main cause of positive electrode chemical property difference.First-principles calculations result then shows LiMBO 3for insulator, its band gap width is all greater than 3eV.Therefore, as LiFePO 4the same Deng polyanionic positive electrode, restriction LiMBO 3the major defect of performance is low lithium ion diffusion coefficient and electronic conductivity, is up to the present still considered to one of characteristic of polyanionic positive electrode.Therefore, carbon is coated has been applied to improving LiMnBO with methods such as reducing material particle size 3electro-chemical activity.As the LiMnBO prepared for carbon source with carbon gel 3/ C composite, between 2-4.2V, 0.05mA/cm 2under, obtain the specific capacity of 20mAh/g.By the carbon black of high-specific surface area and LiMnBO 3after ball milling, LiMnBO 3chemical property also improve, when 10mA/g current density, first discharge specific capacity is 82.5mAh/g, and the capability retention after 25 weeks that circulates is 74.7%.These results show, when material granule is larger, as the LiMnBO of high temperature solid-state method synthesis 3material particle size is up to 7 microns, and material electrochemical activity is very poor, and specific discharge capacity is far below its theoretical specific capacity.This limits Li because bulky grain material has longer ion transport passage +migration, although carbon coating technology can improve the electronic conductivity of material, the ionic conductivity of no less important is not improved.But when their particle size is reduced to nanoscale, all show higher reversible lithium storage capacity, such as, monocline LiMnBO prepared by Ceder group 3nano material is under 2.0-4.5V voltage range, C/20 multiplying power, and first discharge specific capacity is 34mAh/g; After carbon coated, LiMnBO 3/ C nano composite property obviously improves, and can obtain the specific discharge capacity of 100mAh/g under the same conditions, and the specific discharge capacity after 10 times that circulates reduces to 70mAh/g.The hexaplanar LiMnBO of the synthesis such as Afyon 3/ C nano composite material (average grain diameter is about 20nm), in 1.7-4.7V voltage range, under C/20 multiplying power, the first discharge specific capacity of material reaches 136mAh/g, but Capacity fading is fast, and the specific discharge capacity of circulation in the 10th week drops to 80mAh/g.In order to address this problem, they have prepared LiMnBO by ball milling 3/ graphene nanocomposite material, first discharge specific capacity is increased to 145mAh/g, and the specific discharge capacity of circulation in the 10th week remains on 111mAh/g.As can be seen here, LiMBO 3as electrode material, good chemical property be had, lithium ion transport fast and electronics transport must be met simultaneously.Therefore, need to find one and can improve LiMnBO 3electronic conductivity can improve again the method for its lithium ion diffusion rate, obtains good chemical property.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion battery LiMnBO 3/ KB composite positive pole and preparation method thereof, makes this composite positive pole not only have high conductivity, also has high-lithium ion diffusion rate, thus obtain excellent chemical property.
The object of the invention is to realize by the following technical solutions:
A kind of lithium ion battery LiMnBO 3/ KB composite positive pole, LiMnBO 3content is the 55wt% ~ 85wt% of composite material, KB content is the 15wt% ~ 45wt% of composite material, LiMnBO 3the skeleton being distributed in KB with particle and/or film morphology forms composite material.
Above-mentioned lithium ion battery LiMnBO 3the preparation method of/KB composite positive pole, comprises the following steps:
(1), by soluble in water for soluble manganese salt, be mixed with the solution that mass percent concentration is 36% ~ 65%;
(2), by soluble in water for Soluble oxalate salt, be mixed with the solution that mass percent concentration is 4% ~ 12%;
(3) dried Ketjen black (KB) is joined in the solution that (1) step obtain and flood, then the lock out operation such as suction filtration, centrifugal or press filtration are carried out to suspension, obtain Solid separate;
(4) the Solid separate that (3) step obtains is joined in the solution that (2) step obtain and carry out deposition reaction 10 ~ 30 minutes, then lock out operation and the washings such as suction filtration, centrifugal or press filtration are carried out to suspension, at 80 DEG C, after drying, obtain Solid separate;
(5) after the Fe content in the Solid separate that (4) obtains of determination step, (4) step is obtained Solid separate and lithium source, boron source by Mn: Li: B the ratio 1: 1: 1 of amount of substance or and LiBO 2the ratio of the amount of substance by 1: 1 mixes, and then sinters in inert atmosphere stove, then is cooled to room temperature, then obtain LiMnBO 3/ KB composite positive pole.
Above-mentioned LiMnBO 3the preparation method of/KB composite positive pole, the Solid separate that described step (3) obtains first joins in the solution that (1) step obtain and floods, and joins in the solution that (2) step obtain again and carry out step deposition reaction (4) after being separated.
Above-mentioned LiMnBO 3the preparation method of/KB composite positive pole, LiMnBO 3the skeleton being distributed in Ketjen black with particle and (or) film morphology forms composite material.LiMnBO in described composite material 3content be the 55wt% ~ 85wt% of composite material, Ketjen black content is the 15wt% ~ 45wt% of composite material.
Above-mentioned LiMnBO 3the preparation method of/KB composite positive pole, described soluble manganese salt is the one in manganese nitrate, manganese sulfate, manganese chloride, manganese acetate.
Above-mentioned LiMnBO 3the preparation method of/KB composite positive pole, described Soluble oxalate salt is the one in ammonium oxalate or sodium oxalate.
Above-mentioned LiMnBO 3the preparation method of/KB composite positive pole, described lithium source is the one in lithium nitrate, lithium carbonate, lithium acetate.
Above-mentioned LiMnBO 3the preparation method of/KB composite positive pole, described boron source is the one in boric acid, borate.
Above-mentioned LiMnBO 3the preparation method of/KB composite positive pole, described step sintering temperature is (5) 500 ~ 800 DEG C; Sintering time is 5 ~ 10h.
Beneficial effect of the present invention is:
Preparation technology of the present invention is simple, and process is easy to control, the LiMnBO prepared 3/ KB composite material has higher specific discharge capacity, excellent cyclical stability and high rate performance.LiMnBO 3/ KB composite material is under C/40, C/20, C/10, C/5 multiplying power, and first discharge specific capacity is respectively 127,114,112 and 98mAh/g.Under C/20, C/10 multiplying power, after circulation in 30 weeks, specific discharge capacity is respectively 114 and 94mAh/g.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 sample X ray diffracting spectrum.
Fig. 2 is the embodiment of the present invention 1 Sample Scan Electronic Speculum figure.
Fig. 3 is the charging and discharging curve of embodiment 1 under different multiplying, discharge and recharge system: C/40 multiplying power, voltage range 1.7-4.5V, constant-current constant-voltage charging (cut-off current is 1mA/g).
Fig. 4 is the charging and discharging curve of embodiment 1 under different multiplying, discharge and recharge system: C/5 multiplying power, voltage range 1.7-4.5V, constant-current constant-voltage charging (cut-off current is 1mA/g).
Fig. 5 is the cycle performance figure of embodiment 1, discharge and recharge system: voltage range 1.7-4.5V, constant-current constant-voltage charging (cut-off current is 1mA/g).
Fig. 6 is embodiment 1 cycle performance figure under different multiplying.
Embodiment
In order to understand the present invention better, below in conjunction with embodiment and accompanying drawing, the invention will be further described, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
LiMnBO of the present invention 3the preparation method of/KB composite positive pole, comprises the steps:
(1) take the manganese nitrate solution of 13.2816 gram 50%.
(2) 4.5224 grams of ammonium oxalate are dissolved in distilled water, are mixed with the solution that mass percent concentration is 12%.
(3) dried 0.3338 gram of Ketjen black is joined in the solution that (1) step obtain and flood, then the lock out operation such as suction filtration, centrifugal or press filtration are carried out to suspension, obtain Solid separate.
(4) the Solid separate that (3) step obtains is joined in the solution that (2) step obtain and carry out deposition reaction 10 ~ 30 minutes, again lock out operation and the washings such as suction filtration, centrifugal or press filtration are carried out to suspension, then the Solid separate obtained is joined in step solution (1) and again flood, after being separated, carrying out step deposition reaction (4) again.Through being separated, washing, obtain Solid separate after drying at 80 DEG C.
(5) after the Fe content in the Solid separate that (4) obtains of determination step, (4) step is obtained Solid separate to mix by the ratio 1: 1: 1 of the amount of substance of Mn: Li: B with lithium acetate, boric acid, then 350 DEG C of insulation 10h, 500 DEG C of insulation 10h in argon gas atmosphere, be cooled to room temperature again, then obtain LiMnBO 3/ KB composite positive pole (LiMnBO 3content is 60.11wt%).The product of embodiment 1 adopts BruckerD8Advance type X-ray diffractometer, JMS-6380LV type scanning electron microscopy measures.X-ray diffraction and Analysis of Surface Topography are respectively as shown in Figure 1, 2.
Fig. 1 shows the LiMnBO prepared by embodiment 1 3diffraction spectrogram and PDF card match, and material phase analysis shows that synthesized sample has hexagonal structure.Do not detect the diffraction maximum of KB in collection of illustrative plates, the carbon in illustrative material exists with unbodied form.As shown in Figure 2, LiMnBO 3distribution of particles in the network configuration of KB, due to LiMnBO 3/ KB compound is made up of closelypacked aggregate, so be difficult to estimate LiMnBO 3granular size.
Carried out charge-discharge test and cycle performance test to the product of embodiment 1, result is respectively as shown in Fig. 3,4,5,6.Can find out, the LiMnBO of preparation 3/ KB composite material is under C/40, C/20, C/10, C/5 multiplying power, and first discharge specific capacity is respectively 127,114,112 and 98mAh/g.Under C/20, C/10 multiplying power, after circulation in 30 weeks, specific discharge capacity is respectively 114 and 94mAh/g.The above results shows, the LiMnBO prepared 3/ KB composite material has higher specific discharge capacity, excellent cyclical stability and high rate performance.
Embodiment 2
LiMnBO of the present invention 3the preparation method of/KB composite positive pole, comprises the steps:
(1) 6.3547 grams of manganese nitrate solution distilled water are dissolved, be mixed with the solution that mass percent concentration is 65%.
(2) 4.1365 grams of ammonium oxalate are dissolved in distilled water, are mixed with the solution that mass percent concentration is 9%.
(3) dried 0.3632 gram of Ketjen black is joined in the solution that (1) step obtain and flood, then the lock out operation such as suction filtration, centrifugal or press filtration are carried out to suspension, obtain Solid separate.
(4) the Solid separate that (3) step obtains is joined in the solution that (2) step obtain and carry out deposition reaction 10 ~ 30 minutes, then lock out operation and the washings such as suction filtration, centrifugal or press filtration are carried out to suspension, at 80 DEG C, after drying, obtain Solid separate.
(5) after the Fe content in the Solid separate that (4) obtains of determination step, (4) step is obtained Solid separate to mix by the ratio 1: 1: 1 of the amount of substance of Mn: Li: B with lithium acetate, boric acid, then 350 DEG C of insulation 10h, 600 DEG C of insulation 8h in argon gas atmosphere, be cooled to room temperature again, then obtain LiMnBO 3/ KB composite positive pole (LiMnBO 3content is 55wt%).
Embodiment 3
LiMnBO of the present invention 3the preparation method of/KB composite positive pole, comprises the steps:
(1) by 20.2974 grams of MnSO 4h 2o distilled water dissolves, and is mixed with the solution that mass percent concentration is 36%.
(2) 13.6320 grams of ammonium oxalate are dissolved in distilled water, are mixed with the solution that mass percent concentration is 8%.
(3) dried 1.0356 grams of Ketjen blacks are joined in the solution that (1) step obtain and flood, then the lock out operation such as suction filtration, centrifugal or press filtration are carried out to suspension, obtain Solid separate.
(4) the Solid separate that (3) step obtains is joined in the solution that (2) step obtain and carry out deposition reaction 10 ~ 30 minutes, again suction filtration, washing are carried out to suspension, then the Solid separate obtained is joined in step solution (1) and again flood, after being separated, carrying out step deposition reaction (4) again.Circulation like this three times.Through being separated, washing, obtain Solid separate after drying at 80 DEG C.
(5), after the Fe content in the Solid separate that (4) obtains of determination step, (4) step is obtained Solid separate and LiBO 2mix by the ratio 1: 1 of amount of substance, then 350 DEG C of insulation 10h, 800 DEG C of insulation 5h in argon gas atmosphere, then be cooled to room temperature, then obtain LiMnBO 3/ KB composite positive pole (LiMnBO 3content is 85wt%).
Embodiment 4
LiMnBO of the present invention 3the preparation method of/KB composite positive pole, comprises the steps:
(1) by 6.2587 grams of MnCl 2dissolve with distilled water, be mixed with the solution that mass percent concentration is 50%.
(2) 4.5224 grams of sodium oxalates are dissolved in distilled water, are mixed with the solution that mass percent concentration is 4%.
(3) dried 0.3235 gram of Ketjen black is joined in the solution that (1) step obtain and flood, then the lock out operation such as suction filtration, centrifugal or press filtration are carried out to suspension, obtain Solid separate.
(4) the Solid separate that (3) step obtains is joined in the solution that (2) step obtain and carry out deposition reaction 10 ~ 30 minutes, again lock out operation and the washings such as suction filtration, centrifugal or press filtration are carried out to suspension, then the Solid separate obtained is joined in step solution (1) and again flood, after being separated, carrying out step deposition reaction (4) again.Through being separated, washing, obtain Solid separate after drying at 80 DEG C.
(5) after the Fe content in the Solid separate that (4) obtains of determination step, (4) step is obtained Solid separate to mix by the ratio 1: 1: 1 of the amount of substance of Mn: Li: B with lithium acetate, butyl borate, then 350 DEG C of insulation 10h, 500 DEG C of insulation 10h in argon gas atmosphere, be cooled to room temperature again, then obtain LiMnBO 3/ KB composite positive pole (LiMnBO 3content is 67wt%).
Embodiment 5
LiMnBO of the present invention 3the preparation method of/KB composite positive pole, comprises the steps:
(1) by 6.2587 grams of Mn (CH 3cOO) 2dissolve with distilled water, be mixed with the solution that mass percent concentration is 50%.
(2) 4.5224 grams of sodium oxalates are dissolved in distilled water, are mixed with the solution that mass percent concentration is 4%.
(3) dried 0.3235 gram of Ketjen black is joined in the solution that (1) step obtain and flood, then the lock out operation such as suction filtration, centrifugal or press filtration are carried out to suspension, obtain Solid separate.
(4) the Solid separate that (3) step obtains is joined in the solution that (2) step obtain and carry out deposition reaction 10 ~ 30 minutes, again lock out operation and the washings such as suction filtration, centrifugal or press filtration are carried out to suspension, then the Solid separate obtained is joined in step solution (1) and again flood, after being separated, carrying out step deposition reaction (4) again.Through being separated, washing, obtain Solid separate after drying at 80 DEG C.
(5) after the Fe content in the Solid separate that (4) obtains of determination step, (4) step is obtained Solid separate to mix by the ratio 1: 1: 1 of the amount of substance of Mn: Li: B with lithium acetate, butyl borate, then 350 DEG C of insulation 10h, 500 DEG C of insulation 10h in argon gas atmosphere, be cooled to room temperature again, then obtain LiMnBO 3/ KB composite positive pole (LiMnBO 3content is 64wt%).
Embodiment 6
LiMnBO of the present invention 3the preparation method of/KB composite positive pole, comprises the steps:
(1) take the manganese nitrate solution of 13.2816 gram 50%.
(2) 4.5224 grams of ammonium oxalate are dissolved in distilled water, are mixed with the solution that mass percent concentration is 12%.
(3) dried 0.3469 gram of Ketjen black is joined in the solution that (1) step obtain and flood, then the lock out operation such as suction filtration, centrifugal or press filtration are carried out to suspension, obtain Solid separate.
(4) the Solid separate that (3) step obtains is joined in the solution that (2) step obtain and carry out deposition reaction 10 ~ 30 minutes, again lock out operation and the washings such as suction filtration, centrifugal or press filtration are carried out to suspension, then the Solid separate obtained is joined in step solution (1) and again flood, after being separated, carrying out step deposition reaction (4) again.Through being separated, washing, obtain Solid separate after drying at 80 DEG C.
(5) after the Fe content in the Solid separate that (4) obtains of determination step, (4) step is obtained Solid separate to mix by the ratio 1: 1: 1 of the amount of substance of Mn: Li: B with lithium carbonate, boric acid, then 350 DEG C of insulation 10h, 550 DEG C of insulation 9h in argon gas atmosphere, be cooled to room temperature again, then obtain LiMnBO 3/ KB composite positive pole (LiMnBO 3content is 61wt%).
Embodiment 7
LiMnBO of the present invention 3the preparation method of/KB composite positive pole, comprises the steps:
(1) by 6.2587 grams of MnCl 2dissolve with distilled water, be mixed with the solution that mass percent concentration is 50%.
(2) 4.5224 grams of sodium oxalates are dissolved in distilled water, are mixed with the solution that mass percent concentration is 4%.
(3) dried 0.3418 gram of Ketjen black is joined in the solution that (1) step obtain and flood, then the lock out operation such as suction filtration, centrifugal or press filtration are carried out to suspension, obtain Solid separate.
(4) the Solid separate that (3) step obtains is joined in the solution that (2) step obtain and carry out deposition reaction 10 ~ 30 minutes, again lock out operation and the washings such as suction filtration, centrifugal or press filtration are carried out to suspension, then the Solid separate obtained is joined in step solution (1) and again flood, after being separated, carrying out step deposition reaction (4) again.Through being separated, washing, obtain Solid separate after drying at 80 DEG C.
(5) after the Fe content in the Solid separate that (4) obtains of determination step, (4) step is obtained Solid separate to mix by the ratio 1: 1: 1 of the amount of substance of Mn: Li: B with lithium nitrate, boric acid, then 350 DEG C of insulation 10h, 700 DEG C of insulation 70h in argon gas atmosphere, be cooled to room temperature again, then obtain LiMnBO 3/ KB composite positive pole (LiMnBO 3content is 68.3wt%).
Below be only preferred embodiment of the present invention, according to above-mentioned design of the present invention, those skilled in the art can also make various amendment and conversion to this, such as, in the proportioning provided in the present invention and process condition range, combine proportioning and process conditions, convert, these similar conversion and amendment all belong to essence of the present invention.

Claims (8)

1. a lithium ion battery LiMnBO 3/ KB composite positive pole, is characterized in that: LiMnBO 3content is the 55wt% ~ 85wt% of composite material, KB content is the 15wt% ~ 45wt% of composite material, LiMnBO 3the skeleton being distributed in KB with particle and/or film morphology forms composite material, and described KB represents Ketjen black.
2. lithium ion battery LiMnBO according to claim 1 3the preparation method of/KB composite positive pole, is characterized in that comprising the following steps:
(1), by soluble in water for soluble manganese salt, be mixed with the solution that mass percent concentration is 37% ~ 65%;
(2), by soluble in water for Soluble oxalate salt, being mixed with mass percent concentration is 4% ~ 12% solution;
(3) dried KB is joined in the solution that (1) step obtain and flood, then suction filtration, centrifugal or press filtration are carried out to suspension, obtain Solid separate;
(4) the Solid separate that (3) step obtains is joined in the solution that (2) step obtain and carry out deposition reaction 10 ~ 30 minutes, then suction filtration, centrifugal or press filtration and washing are carried out to suspension, at 80 DEG C, after drying, obtain Solid separate;
(5) after the Fe content in the Solid separate that (4) obtains of determination step, the Solid separate that (4) step is obtained and lithium source, boron source by Mn: Li: B the ratio 1: 1: 1 of amount of substance or and LiBO 2the ratio of the amount of substance by 1: 1 mixes, and then sinters in inert atmosphere stove, then is cooled to room temperature, then obtain LiMnBO 3/ KB composite positive pole.
3. lithium ion battery LiMnBO according to claim 2 3the preparation method of/KB composite positive pole, it is characterized in that: the Solid separate that described step (3) obtains first joins in the solution that (1) step obtain and floods, join again after being separated in the solution that (2) step obtain and carry out step deposition reaction (4).
4. the lithium ion battery LiMnBO according to Claims 2 or 3 3the preparation method of/KB composite positive pole, is characterized in that: described soluble manganese salt is the one in manganese nitrate, manganese sulfate, manganese chloride or manganese acetate.
5. the lithium ion battery LiMnBO according to Claims 2 or 3 3the preparation method of/KB composite positive pole, is characterized in that: described Soluble oxalate salt is the one in ammonium oxalate or sodium oxalate.
6. the lithium ion battery LiMnBO according to Claims 2 or 3 3the preparation method of/KB composite positive pole, is characterized in that: described lithium source is the one in lithium nitrate, lithium carbonate or lithium acetate.
7. the lithium ion battery LiMnBO according to Claims 2 or 3 3the preparation method of/KB composite positive pole, is characterized in that: described boron source is the one in boric acid, borate.
8. the lithium ion battery LiMnBO according to Claims 2 or 3 3the preparation method of/KB composite positive pole, is characterized in that: described step sintering temperature is (3) 500 ~ 800 DEG C; Sintering time is 5 ~ 10h.
CN201410195633.2A 2014-05-09 2014-05-09 A kind of lithium ion battery LiMnBO 3/ KB composite positive pole and preparation method thereof Expired - Fee Related CN103943857B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410195633.2A CN103943857B (en) 2014-05-09 2014-05-09 A kind of lithium ion battery LiMnBO 3/ KB composite positive pole and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410195633.2A CN103943857B (en) 2014-05-09 2014-05-09 A kind of lithium ion battery LiMnBO 3/ KB composite positive pole and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103943857A CN103943857A (en) 2014-07-23
CN103943857B true CN103943857B (en) 2016-02-03

Family

ID=51191427

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410195633.2A Expired - Fee Related CN103943857B (en) 2014-05-09 2014-05-09 A kind of lithium ion battery LiMnBO 3/ KB composite positive pole and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103943857B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102079530A (en) * 2009-11-29 2011-06-01 宁波大学 Method for preparing lithium iron borate serving as positive material of lithium ion battery by sol-gel technology
WO2013155638A2 (en) * 2012-04-18 2013-10-24 Eth Zurich Reference materials
CN103545508A (en) * 2012-07-09 2014-01-29 国家纳米科学中心 Positive electrode material LiFeBO3 of lithium ion battery and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5013622B2 (en) * 2009-03-09 2012-08-29 独立行政法人産業技術総合研究所 Method for producing lithium borate compound
JP5728721B2 (en) * 2011-10-12 2015-06-03 国立研究開発法人産業技術総合研究所 Heat-resistant lithium ion secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102079530A (en) * 2009-11-29 2011-06-01 宁波大学 Method for preparing lithium iron borate serving as positive material of lithium ion battery by sol-gel technology
WO2013155638A2 (en) * 2012-04-18 2013-10-24 Eth Zurich Reference materials
CN103545508A (en) * 2012-07-09 2014-01-29 国家纳米科学中心 Positive electrode material LiFeBO3 of lithium ion battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Synthesis and electrochemistry of monoclinic Li(MnxFe1-x)BO3: a combined experimental and computational study";Atsuo Yamada et al.;《Journal of Materials Chemistry》;20110622;第21卷;全文 *

Also Published As

Publication number Publication date
CN103943857A (en) 2014-07-23

Similar Documents

Publication Publication Date Title
Aravindan et al. Influence of carbon towards improved lithium storage properties of Li 2 MnSiO 4 cathodes
CN102201576B (en) Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof
CN103400962B (en) A kind of spherical LiFePO 4/ (C+La 2/3-xli 3xtiO 3) composite anode material and preparation method thereof
CN103000888B (en) Lithium ion battery composite cathode material LiMnPO4-Li3V2 (PO4) 3/C and preparation method thereof
CN105226274B (en) A kind of preparation method of the scattered LiFePO4/graphene composite material of graphene uniform
CN106654221A (en) Three-dimensional porous carbon-coated zinc selenide material for lithium ion battery anodes and preparation method of material
CN102496714A (en) Anode active substance, production method thereof, and lithium ion battery employing anode active substance
CN102427131A (en) Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery
CN105355908A (en) Composite negative electrode material for lithium ion battery, preparing method thereof, negative electrode using material and lithium ion battery
CN103855389A (en) Ferric (III) fluoride / carbon composite material and its preparation method and application
CN1971981A (en) High charge-discharge magnification lithium iron phosphate material used for anode of lithium ion battery and its preparation method
CN107275590A (en) A kind of porous Si-C composite material and its preparation method and application
CN104868110B (en) The mesoporous Co of Graphene guiding2V2O7Nanometer sheet material and its preparation method and application
CN104425845A (en) High-energy density lithium ion power battery and manufacturing method thereof
CN102386412A (en) Lithium ion battery anode Li3V2(PO4)3/C composite material and preparation method thereof
CN105226244A (en) Three-dimensional porous silicon-nano silver composite material and preparation thereof and the application as lithium ion battery negative material
CN103296312A (en) Preparation method of large-power high-magnification lithium iron phosphate battery
CN102110811B (en) Method for preparing nanoscale lithium ion battery LiFePo4/C anodal material
CN108134079A (en) The application of ferric phosphate and phosphoric acid iron composite material as cathode in Dual-ion cell
CN105390683A (en) Sulfur-based negative electrode material of lithium ion batteries and application thereof
CN103413944A (en) Lithium manganese phosphate positive electrode material and preparation method thereof
CN103413940B (en) A kind of synthetic method of positive material nano lithium manganese phosphate of lithium ion battery
CN101834287B (en) Preparation method of anode material of lithium ion battery
CN102786048B (en) Method for preparing conductive additive for lithium ion batteries
CN107180944A (en) A kind of preparation method and applications of metal phosphide nano-particle

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
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160203