CN105118982A - Doping modification technology of lithium ion battery positive electrode material - Google Patents
Doping modification technology of lithium ion battery positive electrode material Download PDFInfo
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- CN105118982A CN105118982A CN201510420800.3A CN201510420800A CN105118982A CN 105118982 A CN105118982 A CN 105118982A CN 201510420800 A CN201510420800 A CN 201510420800A CN 105118982 A CN105118982 A CN 105118982A
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- 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
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- 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
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a doping modification technology of a lithium ion battery positive electrode material. The technology comprises the following steps: preprocessing, synthesizing a precursor solution, processing the precursor, carrying out high temperature sintering, depositing transition metal ions on nanometal oxide particles, and carrying out thermal treatment to prepare the precursor in order to modify a positive electrode material. Compared with materials in the prior art, the material synthesized in the material has the advantages of normal spinel cubic structure, no impurity phases, no obvious influences of doping modification on the structure of lithium manganate, and good cycle performance, high temperature storage performance, rate performance and safety performance.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of doping vario-property technology of anode material for lithium-ion batteries.
Background technology
Early 1980s phase, people's Late Cambrian such as American scholar J.B.Goodenough cobalt acid lithium (LiCoO
2), lithium nickelate (LiNiO
2) and LiMn2O4 (LiMn
2o
4) as the material of deintercalate lithium ions, and can apply for patent " Electrochemicalcellwithnewfastionconductors " (US4302518A).Wherein cobalt acid lithium using the chemical property of excellence and good electrode machining performance early 1990s to be successfully applied to by Sony corporation of Japan first in business-like small-sized electronic product lithium ion battery as positive electrode.Although lithium nickelate has very high reversible specific capacity (210mAh/g), its poor structural stability and the reason such as thermal stability and synthesis difficulty, cannot be applied in practical lithium-ion.And the development of power-type lithium ion battery is had higher requirement to positive electrode, as fail safe, cost and cycle performance etc.Cobalt acid lithium, due to its shortcoming such as high cost and poor heat stability, is not suitable as power type lithium-ion battery anode material.
The positive electrode being hopeful most to use in power-type lithium ion battery at present mainly contains modified spinelle manganic acid lithium (LiMn
2o
4), LiFePO 4 (LiFePO
4) and nickel-cobalt-manganese ternary system (Li (Ni, Co, Mn) O
2) material.LiFePO 4 (LiFePO
4) have raw material sources enrich, cost is low, has extended cycle life, structural stability and thermal stability advantages of higher, but its electronics and ionic conductivity are very low, make this material high-rate charge-discharge capability and cryogenic property poor.In addition, also there is product stability and the shortcoming such as consistency is bad and tap density is low, electrode machining poor performance in this material.Nickel-cobalt-manganese ternary system (Li (Ni, Co, Mn) O
2) material utilizes hydroxide co-precipitation presoma to prepare under high temperature sintering by Japanese scholars T.Ohzuku and Canadian scholar J.Dahn at first.This material has higher specific capacity and good structural stability and thermal stability, but also has that cost is higher, tap density is lower and the shortcoming such as electrode machining poor performance.
In order to overcome the many disadvantages of current material existence and improve its performance, bulk phase-doped technology was widely used in the study on the modification of positive electrode before 2000, and achieved positive achievement.In such as LiMn2O4 and lithium nickel cobalt dioxide, magnesium-doped element etc. in adulterated al element and LiFePO4, all has remarkable result to the raising of material property.After 2000, along with various scholars going deep into investigation of materials, find the surface nature of positive electrode particle on its physics and chemical property particularly very large on the impact of cycle performance and high-temperature behavior, therefore the coating modification on positive electrode surface becomes the hot fields of research.Researcher's many employings inorganic oxide or phosphate carry out coated and surface modification, as aluminium oxide, magnesium oxide, titanium oxide and aluminum phosphate etc. both at home and abroad at present.Although adopt inorganic oxide or phosphate to carry out coating modification to positive electrode can improve its cycle performance and security performance; but during due to high-temperature heat treatment; metal oxide or phosphate crystal grain can be grown up and be reacted with positive electrode; the surface area of coated rear material is often caused to increase; the problems such as capacity reduction and consistency difference, are therefore seldom used in actual production.
Chinese patent CN104112860A discloses the material modified preparation method of a kind of lithium ion cell positive, and cell positive material is carried out ball milling 5-10 hour with the ratio of grinding media to material of 1-2:1, then at 900 DEG C-1200 DEG C, calcines 3-5 hour, obtains just material; Then by just material carry out rare earth doped; Finally adopting Nano Silver, coated to obtain lithium ion cell positive material modified, and the obtained positive electrode fail safe of the method is high, and energy density is high, and lithium ion conductivity is high, but uses traditional material to process, and causes capacity to reduce, the problem that stability is not high.Chinese patent CN104009216A discloses the material modified and preparation method thereof of a kind of lithium ion cell positive, anode material for lithium-ion batteries is coated with the praseodymium oxide that mass fraction is 3-7%, the material modified chemical formula of the lithium ion cell positive after coated praseodymium oxide is: Li
1.17[Ni
0.21co
0.12mn
0.67]
0.83o
2/ Pr
6o
11; This material has larger specific discharge capacity, excellent multiplying power discharging, and cycle performance is better, but praseodymium oxide price is high, for high cost lithium ion battery, is unfavorable for marketplace trend.
Summary of the invention
The problem of power-type lithium ion battery requirement cannot be reached to solve positive electrode performance in lithium ion battery industry, we have proposed a kind of doping vario-property technology of anode material for lithium-ion batteries, adopt the present invention can strengthen the electrode machining performance of positive electrode, cycle performance, high-temperature storage performance and security performance, meet high performance lithium ion battery, particularly the instructions for use of power-type lithium ion battery.
The present invention is achieved by the following technical solutions:
For achieving the above object, the invention provides a kind of doping vario-property technology of anode material for lithium-ion batteries, step is as follows:
(1) preliminary treatment: add nano modification metal oxide and be made into solid-liquid mixture in transition metal solution, mix and blend 10-30 minute.Wherein transition metal solution solute and nano modification metal oxide mass ratio are 30-1000:1; Transition metal solution is sulfate, at least one in nitrate and chlorate; Nano modification metal oxide is aluminium oxide, magnesium oxide, titanium oxide, at least one in calcium oxide and zirconia.
(2) precursor solution is synthesized: by pretreated solid-liquid mixture in step (1) and the solution hybrid reaction in a kettle. containing precipitation reagent, make transition metal ions be deposited on metal oxide nano particles, prepare composite doping modification lithium-ion battery anode material precursor solution.Precipitation reagent is NaOH, potassium hydroxide, sodium carbonate, at least one in the alkali-metal hydroxide such as potash or carbonate.The cation of anion in precipitation reagent in transition metal solution is combined, and produces precipitation, and deposition is attached on nano-metal-oxide, forms solid mixture.
(3) presoma process: by precursor solution filtration washing in step (2), obtain solid mixture, solid mixture is heat-treated at 100-600 DEG C, after cooling according to mole metering of lithium and metal 0.5-1.5:1 than adding lithium salts, in material grinder, carry out mixed grinding.
(4) high temperature sintering: by the powder after having ground under oxidizing atmosphere environment, sinter 12-36 hour at 800-1200 DEG C, obtains doping vario-property positive electrode.
Preferably, above-mentioned positive electrode, mainly includes, but are not limited to cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, the rich lithium height manganese solid solution of stratiform and their doped derivatives.
Preferably, the concentration of above-mentioned transition metal solution is 1-5 mol/L.
Preferably, the above-mentioned solution concentration containing precipitation reagent is 1-5 mol/L.
Preferably, above-mentioned lithium salts is at least one in lithium carbonate, lithium hydroxide.
Compared with prior art, beneficial effect of the present invention is:
1, better cycle performance, high-temperature storage performance, high rate performance and security performance is had.
Accompanying drawing explanation
Fig. 1 is the charging and discharging curve figure that positive electrode of the present invention makes lithium manganate battery;
Fig. 2 is the charging and discharging curve figure of commercial lithium manganate battery;
Fig. 3 is the charging and discharging curve figure of the nickle cobalt lithium manganate tertiary cathode material that the inventive method makes;
Fig. 4 is the charging and discharging curve figure of commercial nickle cobalt lithium manganate tertiary cathode material;
Fig. 5 is the X ray diffracting spectrum of the modified lithium manganate that the present invention makes.
Embodiment
Below in conjunction with embodiment, further illustrate content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention or change all fall into scope; And the method in following embodiment, if no special instructions, be the conventional method of this area.
Embodiment 1:
A doping vario-property technology for anode material for lithium-ion batteries, step is as follows:
45 kilograms of manganese sulfates are dissolved in water, are made into the solution of 2 mol/L.Then by 1 kilogram of nanometer Al
2o
3join in the aqueous solution of manganese sulfate and carry out stirring 15 minutes, prepare mixed solution.The sodium carbonate of 28.5 kilograms is dissolved in water, is made into the solution of 2 mol/L, as precipitation reagent.Use measuring pump mixing manganese sulfate solution and sodium carbonate liquor to be input in reactor simultaneously and carry out chemical reaction, generate carbonic acid manganese deposition on nano alumina particles.By solidliquid mixture filtration washing, obtain the solid mixture of manganese carbonate and aluminium oxide.
Again by the heat treatment under 450 degree of this solid mixture, generating manganese oxide and alumina composite oxide precursor, according to mole metering of lithium and metallic element 1:2 than adding lithium carbonate, in material grinder, carrying out mixed grinding.Finally ground powder is sintered under 900 degree the aluminium doping vario-property manganate cathode material for lithium required for obtaining for 24 hours.
In order to measure the chemical property of this material, the electroactive substance of above-mentioned synthesis, acetylene black and PVDF (Kynoar) are mixed to form slurry at normal temperatures and pressures according to the ratio of 85:10:5, even application is in aluminum substrates. after the electrode slice obtained is dried at 140 DEG C, compress under pressure, continue to dry 12 hours at 140 DEG C, then film being cut into area is 1cm
2thin rounded flakes as positive pole.Be negative pole with pour lithium slice, think 1mol/lLiPF
6eC+DMC (volume ratio 1:1) electrolyte, is assembled into experimental cell in the glove box being full of argon gas, carries out charge and discharge cycles test to it, and experimental cell carries out charge and discharge cycles test by by computer-controlled auto charge and discharge instrument.Charging and discharging currents is 100mA/g, and charge cutoff voltage is 4.35V, and discharge cut-off voltage is 3.0V, and the 3rd week discharge and recharge result as shown in figure 1 and table 1; Simultaneously under 45 DEG C of stable hot conditionss, carry out charge-discharge test, result is as shown in table 2.
Embodiment 2:
A doping vario-property technology for anode material for lithium-ion batteries, step is as follows:
45 kilograms of cobaltous sulfates are dissolved in water, are made into the solution of 2 mol/L.Then 0.5 kilogram of nano-MgO is joined in the aqueous solution of cobaltous sulfate and carry out stirring 15 minutes, prepare mixed solution.The NaOH of 21.5 kilograms is dissolved in water, is made into the solution of 2 mol/L, as precipitation reagent.Use measuring pump mix sulphur acidic cobalt solution and sodium carbonate liquor to be input in reactor simultaneously and carry out chemical reaction, generate cobalt carbonate and be deposited on nano oxidized magnesium granules.By solidliquid mixture filtration washing, obtain manganese carbonate and magnesian solid mixture.
Again by the heat treatment under 450 degree of this solid mixture, generating manganese oxide and magnesium oxide composite oxides precursor, according to mole metering of lithium and metallic element 1:1 than adding lithium carbonate, in material grinder, carrying out mixed grinding.Finally ground powder is sintered under 1000 degree the magnesium doping vario-property lithium cobaltate cathode material required for obtaining for 16 hours.
Testing procedure is substantially the same manner as Example 1.
Embodiment 3:
A doping vario-property technology for anode material for lithium-ion batteries, step is as follows:
8 kilograms of cobaltous sulfates and 37 kilograms of nickelous sulfates are dissolved in water simultaneously, are made into the solution of 2 mol/L.Then by 1 kilogram of nanometer Al
2o
3join in the aqueous solution of cobaltous sulfate and nickelous sulfate and carry out stirring 15 minutes, prepare mixed solution.The sodium carbonate of 28 kilograms is dissolved in water, is made into the solution of 2 mol/L, as precipitation reagent.Use measuring pump mixing cobaltous sulfate nickel sulfate solution and sodium carbonate liquor to be input in reactor simultaneously and carry out chemical reaction, generate cobalt carbonate cobalt carbonate and be deposited on nano alumina particles.By solidliquid mixture filtration washing, obtain the solid mixture of nickelous carbonate cobalt carbonate and aluminium oxide.
Again by the heat treatment under 450 degree of this solid mixture, generating cobalt oxide nickel oxide and alumina composite oxide precursor, according to mole metering of 1:1 than adding lithium carbonate, in material grinder, carrying out mixed grinding.Finally ground powder is sintered under 850 degree the aluminium doping vario-property lithium nickel cobalt dioxide positive electrode required for obtaining for 15 hours.
Testing procedure is substantially the same manner as Example 1.
Embodiment 4:
A doping vario-property technology for anode material for lithium-ion batteries, step is as follows:
By 12 kilograms of manganese sulfates, the nickelous sulfate of 13 kilograms of cobaltous sulfates and 20 kilograms is dissolved in water simultaneously, is made into the solution of 2 mol/L.Then by 0.45 kilogram of nanometer Al
2o
3join in the aqueous solution of cobaltous sulfate and nickelous sulfate and carry out stirring 15 minutes, prepare mixed solution.The sodium carbonate of 28 kilograms is dissolved in water, is made into the solution of 2 mol/L, as precipitation reagent.Use measuring pump transition metal solution and sodium carbonate liquor to be input in reactor simultaneously and carry out chemical reaction, generate transition metal carbonate and be deposited on nano alumina particles.By solidliquid mixture filtration washing, obtain the solid mixture of transition metal carbonate and aluminium oxide.
Again by the heat treatment under 450 degree of this solid mixture, generating transition metal oxide and alumina composite oxide precursor, according to mole metering of 1:1 than adding lithium carbonate, in material grinder, carrying out mixed grinding.Finally ground powder is sintered under 950 degree the aluminium doping vario-property lithium nickel cobalt dioxide positive electrode required for obtaining for 15 hours.
Testing procedure is substantially the same manner as Example 1.Result as shown in Figure 3.
Comparative example 1:
Commercial lithium manganate cell positive electrode material, testing procedure is substantially the same manner as Example 1.Result as shown in Figure 2.
Comparative example 2:
Commercial nickle cobalt lithium manganate ternary cell positive material, testing procedure is substantially the same manner as Example 1.Result as shown in Figure 4.
From Fig. 1 and Fig. 2, after using the technology of the present invention to modify, the original spinelle 4.0 of material can not be distinguished with 4.15V platform, and becomes a smooth curve, and the stability of battery is higher, and initial capacitance is higher than commercial common batteries, have better storge quality.
From Fig. 3 and Fig. 4, the cobalt nickel lithium manganate ternary material after using the technology of the present invention to modify, capacity attenuation is comparatively slow, and cycle performance is comparatively strong, and polarize less, high rate performance is better, and capacity is also relatively high.
From in the XRD collection of illustrative plates of Fig. 5 modified lithium manganate, the material of synthesis has positive spinel cubic structure, and free from admixture exists mutually, and namely doping vario-property is on the not too large impact of the structure of LiMn2O4.And modified lithium manganate forms LiAlO after de-lithium in the charge state
2-MnO
2solid solution, the Al-O key stable due to it and LiAlO
2existence, the MnO that formed after making it can take off lithium than pure LiMn2O4
2there is higher structural stability and thermal stability.
Table 1:
| Charging and discharging currents | Circulate 100 times | Circulate 500 times | |
| Embodiment 1 | 1C | 98.9±0.3％ | 97.8±0.4％ |
| 5C | 98.3±0.6％ | 97.5±0.6％ | |
| 10C | 98.0±0.7％ | 97.2±0.5％ | |
| Embodiment 2 | 1C | 99.0±0.2％ | 97.9±0.5％ |
| 5C | 98.5±0.4％ | 97.7±0.4％ | |
| 10C | 98.2±0.7％ | 97.3±0.7％ | |
| Embodiment 3 | 1C | 99.1±0.2％ | 98.0±0.3％ |
| 5C | 98.6±0.4％ | 97.8±0.4％ | |
| 10C | 98.3±0.8％ | 97.3±0.8％ | |
| Embodiment 4 | 1C | 99.5±0.3％ | 99.0±0.2％ |
| 5C | 99.1±0.4％ | 98.2±0.7％ | |
| 10C | 98.8±0.9％ | 97.9±0.6％ | |
| Comparative example 1 | 1C | 97.8±0.5％ | 93.7±0.9％ |
| 5C | 97.3±0.8％ | 93.4±0.8％ | |
| 10C | 97.1±1.0％ | 93.0±0.9％ | |
| Comparative example 2 | 1C | 97.9±0.3％ | 93.8±1.0％ |
| 5C | 97.5±0.7％ | 93.1±1.1％ | |
| 10C | 97.3±0.6％ | 93.4±0.9％ |
As shown in Table 1, adopt the lithium ion battery that method of the present invention makes, with common commercial lithium ion battery, under each charging and discharging currents, the circulation of a small amount of number of times all can ensure higher capacity, and after repeatedly cycle charge-discharge, the lithium ion battery that the inventive method makes has higher capability retention, and under different electric current capacity stablizes, high rate performance is splendid.Table 1 result describes the doping in positive electrode modification technology that the present invention uses, and greatly can improve the chemical property of lithium ion battery, ensures the height circulation of lithium ion battery, long-life, excellent high rate performance and high security.
Table 2:
| Charging and discharging currents | 45 DEG C circulate 100 times | 45 DEG C circulate 500 times | |
| Embodiment 1 | 1C | 95.8±0.2％ | 90.4±0.3％ |
| 5C | 94.5±0.6％ | 90.1±0.7％ | |
| 10C | 90.6±0.8％ | 86.2±0.9％ | |
| Embodiment 2 | 1C | 96.6±0.4％ | 91.2±0.4％ |
| 5C | 94.8±0.6％ | 90.7±0.6％ | |
| 10C | 90.9±0.9％ | 87.1±0.8％ | |
| Embodiment 3 | 1C | 96.9±0.3％ | 91.4±0.5％ |
| 5C | 93.7±0.6％ | 90.1±0.7％ | |
| 10C | 90.3±0.8％ | 85.8±0.9％ | |
| Embodiment 4 | 1C | 96.3±0.7％ | 91.2±0.7％ |
| 5C | 94.1±0.5％ | 90.6±0.9％ | |
| 10C | 90.2±0.4％ | 86.1±0.8％ | |
| Comparative example 1 | 1C | 92.1±0.7％ | 87.0±2.0％ |
| 5C | 88.6±0.9％ | 84.6±1.8％ | |
| 10C | 84.3±1.4％ | 81.3±0.9％ | |
| Comparative example 2 | 1C | 91.7±0.5％ | 87.5±4.7％ |
| 5C | 87.3±0.9％ | 84.1±3.1％ | |
| 10C | 83.6±1.5％ | 80.0±4.1％ |
As shown in Table 2, adopt the lithium ion battery that method of the present invention makes, with common commercial lithium ion battery, charge-discharge test is carried out at 45 DEG C of high temperature, under each charging and discharging currents, the circulation of a small amount of number of times all can ensure higher capacity, and after repeatedly cycle charge-discharge, the lithium ion battery that the inventive method makes has higher capability retention, and better stability.Table 2 result describes the doping in positive electrode modification technology that the present invention uses, and greatly can improve the chemical property of lithium ion battery, ensures the height circulation of lithium ion battery, long-life and thermal stability.
Claims (5)
1. a doping vario-property technology for anode material for lithium-ion batteries, it is characterized in that, step is as follows:
(1) preliminary treatment: add nano modification metal oxide and be made into solid-liquid mixture in transition metal solution, mix and blend 10-30 minute, wherein transition metal solution solute and nano modification metal oxide mass ratio are 30-1000:1; Described transition metal solution is sulfate, at least one in nitrate and chlorate; Described nano modification metal oxide is aluminium oxide, magnesium oxide, titanium oxide, at least one in calcium oxide and zirconia;
(2) precursor solution is synthesized: by pretreated solid-liquid mixture in step (1) and the solution hybrid reaction in a kettle. containing precipitation reagent, make transition metal ions be deposited on metal oxide nano particles, prepare composite doping modification lithium-ion battery anode material precursor solution; Described precipitation reagent is NaOH, potassium hydroxide, sodium carbonate, at least one in the alkali-metal hydroxide such as potash or carbonate;
(3) presoma process: by precursor solution filtration washing in step (2), obtain solid mixture, solid mixture is heat-treated at 100-600 DEG C, after cooling according to mole metering of lithium and metal 0.5-1.5:1 than adding lithium salts, in material grinder, carry out mixed grinding;
(4) high temperature sintering: by the powder after having ground under oxidizing atmosphere environment, sinter 12-36 hour at 800-1200 DEG C, obtains doping vario-property positive electrode.
2. the doping vario-property technology of a kind of anode material for lithium-ion batteries as claimed in claim 1, it is characterized in that, described positive electrode, mainly includes, but are not limited to cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, the rich lithium height manganese solid solution of stratiform and their doped derivatives.
3. the doping vario-property technology of a kind of anode material for lithium-ion batteries as claimed in claim 1, is characterized in that, the concentration of described transition metal solution is 1-5 mol/L.
4. the doping vario-property technology of a kind of anode material for lithium-ion batteries as claimed in claim 1, is characterized in that, the described solution concentration containing precipitation reagent is 1-5 mol/L.
5. the doping vario-property technology of a kind of anode material for lithium-ion batteries as claimed in claim 1, is characterized in that, described lithium salts is at least one in lithium carbonate and lithium hydroxide.
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| CN110034274A (en) * | 2018-01-11 | 2019-07-19 | 宁波纳微新能源科技有限公司 | Modified tertiary cathode material, preparation method and lithium ion battery |
| CN112133903A (en) * | 2020-09-17 | 2020-12-25 | 陕西红马科技有限公司 | Preparation method of cobalt-free cathode material |
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Application publication date: 20151202 |