CN105047924B - A kind of lithium manganese silicate type positive electrode material of lithium ion battery and preparation method thereof - Google Patents
A kind of lithium manganese silicate type positive electrode material of lithium ion battery and preparation method thereof Download PDFInfo
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- H01M4/00—Electrodes
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- 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
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- 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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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The present invention relates to a kind of lithium manganese silicate type positive electrode material of lithium ion battery and preparation method thereof, the chemical general formula of the positive electrode is Li2Mn1‑xMxSiO4/ C, wherein, wherein 0≤x≤0.15, doping metals M is the one or more in Mg, Al, Zn, Cu or Co, and the content of surface coated carbon is 2%~15%.The modified method that the present invention is combined by metal cation doping and carbon coating, effectively improves the structural stability and electronic conductivity of material, there is provided a kind of preferable lithium manganese silicate anode material of cycle performance and high rate performance.The present invention is realized raw material melting or congruent melting, is easily realized that doped chemical is sufficiently mixed with manganese element under congruent melting state at a lower temperature using manganese acetate characteristic low and there are eutectic point with doping M salt fusing points after dry-mixed；Overall preparation process is simple, flow is short, operation is easy, low cost, it is easy to accomplish industrialization large-scale production.
Description
Technical field
The present invention relates to field of lithium ion battery material, and in particular to a kind of lithium manganese silicate type positive electrode material of lithium ion battery
And preparation method thereof.
Background technology
After Japanese Sony companies successfully release commercialized lithium ion battery, lithium ion battery is because of its energy density
It is high, power density is high, have extended cycle life, the pollution-free advantage such as low with self-discharge rate, consumer electronics product, electric tool,
The various fields such as electric automobile, energy-accumulating power station have been widely used.
In numerous crucial compositions of lithium ion battery, positive electrode is to influence battery energy density, power density, circulation
An important factor for service life and security performance, be the part of lithium ion battery most critical.In theory, there is reversible knot
The material for closing the lattice structure of lithium ion can be as the positive electrode of lithium ion battery.Common lithium ion cell positive material
Material can be divided mainly into two major classes.One kind is the transition metal oxide Li of lithiumxMyOz, such material mainly has the cobalt of layer structure
Sour lithium LiCoO2, lithium nickel cobalt dioxide LiNixCoyO2Binary material (ternary material LiNixCoyAlzO2May be regarded as one of which), nickel cobalt
LiMn2O4 LiNixCoyMnzO2Ternary material, lithium-rich manganese-based Li2MnO3·LiMO2Material and spinel structure manganese systems cathode material
Material, such as LiMn2O4 LiMn2O4With nickel ion doped LiNi0.5Mn1.5O4.This kind of material using Lattice Oxygen closs packing as skeleton structure,
Overcharging, short circuit, be also easy to produce the escape of Lattice Oxygen under the extreme condition such as acupuncture and discharge oxygen, cause structure collapses and with it is organic
Redox reaction etc. occurs for electrolyte, and there are serious security risk.Another kind of is containing tetrahedron or octahedra anion
Construction unit (XOm)n-The polyanionic compound of (such as X=P, S, Si), such as olivine-type LiFePO4 LiFePO4。
Extremely strong covalent bond forms polyanion skeleton in such material, is difficult oxygen escape and structure occur during lithium ion deintercalation
Skeleton caves in, and security performance is splendid.
In polyanionic compound, phosphate of olivine type material ferric lithium phosphate is by splendid security performance and fits
In chemical property be applied widely, especially in power battery field, similar lithium manganese phosphate LiMnPO therewith4、
Cobalt phosphate lithium LiCoPO4, LiNiPO LiNiPO4And lithium ferric manganese phosphate LiFexMn1-xPO4It also obtain extensive concern.This
Class material maximum be disadvantageous in that can the lithium ion of deintercalation there was only 1, theoretical specific capacity and available specific capacity are relatively low.Therewith
Compare, in silicates positive electrode can the number of lithium ion of deintercalation be twice of phosphate cathode material, theoretical specific capacity
Up to 330mAh/g.Meanwhile extremely strong silica covalent bond also ensure that and oxygen abjection, peace are less prone to during lithium ion deintercalation
Full excellent performance；Content of the elemental silicon in the earth is only second to oxygen, aboundresources.Therefore, silicate anodal material is expected to become
The anode material for lithium-ion batteries of future generation for most having application prospect after LiFePO4, what research at present was more popular is silicic acid
Iron lithium Li2FeSiO4With manganese silicate of lithium Li2MnSiO4。
2000, Armand et al. proposed that manganese silicate of lithium can be used as lithium ion first in United States Patent (USP) US6085015
The potential positive electrode of battery, 2006, R.Dominko et al. was closed first using citric acid as complexing agent, using sol-gal process
Into lithium manganese silicate anode material.In follow-up research, the preparation of manganese silicate of lithium is that (such as China is specially by sol-gal process mostly
Sharp Authorization Notice No. CN102208602B and CN102394303B etc.), hydro-thermal method (such as Chinese patent Authorization Notice No.
CN101877400B) or solvent-thermal method (such as Chinese patent Authorization Notice No. CN102496717B and CN102646829B etc.),
Complex process used, cost is higher, is unfavorable for industrialized production.Consolidate as high temperature after ball milling common in current industrialized production
The technique of phase sintering, has also reported (such as Chinese patent Authorization Notice No. CN102544478B), but be still employ it is more
The complicated technique of secondary wet ball grinding, solvent seasoning also time and effort consuming.As for the modified aspect of manganese silicate of lithium, due to silicate material
Native electronic conductivity it is very low, cause the chemical property of pure phase silicate material particularly poor, directly limit its application.Mesh
The successful experience of LiFePO4 has also been used for reference in the preceding modification for manganese silicate of lithium, on the basis of particle diameter is controlled, mainly passes through gold
Belong to two kinds of means of ion doping and carbon coating to lift the electronic conductance of material, and then improve its chemical property.
The content of the invention
The purpose of the present invention is：A kind of high electronic conductivity, high structural stability, and cycle performance and high rate performance are provided
Preferable lithium manganese silicate type positive electrode material of lithium ion battery and preparation method thereof.
In order to achieve the above object, the present invention provides following technical solution：
A kind of lithium manganese silicate type positive electrode material of lithium ion battery, the chemical general formula of the positive electrode is Li2Mn1- xMxSiO4/ C, wherein 0≤x≤0.15, doping metals M is the one or more in Mg, Al, Zn, Cu or Co, surface coated carbon
Content be 2%~15%.
The preparation method of the lithium manganese silicate type positive electrode material of lithium ion battery, comprises the following steps：
(1) according to chemical formula Li2Mn1-xMxSiO4Lithium salts, manganese salt, doping M salt and silicon source are weighed in proportion, add carbon source
After carry out dry-mixed, obtain dry-blended mixture；
(2) dry-blended mixture obtained in step (1) is warming up to temperature T1 and kept the temperature, make manganese salt reach molten condition and
M salt and manganese salt congruent melting are adulterated, and realizes fully to infiltrate with other raw materials and mixes；It is continuously heating to temperature T2 and keeps the temperature, makes organic
Carbon source reaches molten condition, and fully infiltrates and mix with other raw materials；It is continuously heating to temperature T3 and keeps the temperature, carries out each raw material
Fully reaction, obtains Preburning material；
(3) it is the Preburning material obtained in step (2) progress is dry-mixed, it is warming up to temperature T4 and keeps the temperature, is sintered reaction.
Preferably, the one kind or more of the lithium salts in step (1) in lithium acetate, lithium nitrate, lithium hydroxide and lithium carbonate
Kind.
Manganese salt in step (1) selects the manganese acetate of low melting point.
One or more of the doped chemical M in Mg, Al, Zn, Cu or Co in step (1), M salt select acetate and
One or more in nitrate.
Silicon source in step (1) selects nano silicon dioxide.
Preferably, the one or more during the carbon source is in glucose, sucrose and polyvinyl alcohol, wherein, most
The mass fraction of end-product surface amorphous carbon is 2%~15%.
Preferably, holding temperature T1 is 80 DEG C~150 DEG C in step (2), and soaking time is 0.5~8h；Protected in step (2)
Temperature T2 is 160 DEG C~250 DEG C, and soaking time is 0.5~8h；Pre-burning holding temperature T3 is 350 DEG C~500 in step (2)
DEG C, soaking time is 1~8h.
Preferably, sintered heat insulating temperature T4 is 650 DEG C~850 DEG C in step (3), and soaking time is 4~20h.
The beneficial effects of the invention are as follows：
The modified method that the present invention is combined by metal cation doping and carbon coating, the structure for effectively improving material are steady
A kind of qualitative and electronic conductivity, there is provided preferable lithium manganese silicate anode material of cycle performance and high rate performance.
The present invention utilizes lower temperature using manganese acetate characteristic low and there are eutectic point with doping M salt fusing points after dry-mixed
Under melting or congruent melting, easily realize that doped chemical is sufficiently mixed with manganese element under congruent melting state；Overall preparation process letter
List, flow is short, operation is easy, low cost, it is easy to accomplish industrialization large-scale production.
Embodiment
Comparative example：Example 1 in molar ratio:1:1 weighs oxide spinel lithium, manganese dioxide and nano silicon dioxide, adds carbon
Dry-mixed after the sucrose of source, the mass fraction that dosage of sucrose is defined to final manganese silicate of lithium material surface carbon residue is 5%.In nitrogen gas
Under atmosphere, mixture is warming up to 450 DEG C of insulation 6h and obtains the Preburning material of manganese silicate of lithium.Preburning material is carried out dry-mixed, continued in nitrogen
Temperature is raised under gas atmosphere to 800 DEG C of insulation 12h, you can obtain lithium manganese silicate anode material Li2MnSiO4/C。
Embodiment 1：Example 1 in molar ratio:1:1 weighs oxide spinel lithium, manganese acetate and nano silicon dioxide, adds carbon source
Dry-mixed after glucose, the mass fraction that glucose dosage is defined to final manganese silicate of lithium material surface carbon residue is 2%.In nitrogen
Under atmosphere, by mixture 80 DEG C keep the temperature 0.5h, rise temperature to 220 DEG C insulation 0.5h, be warming up to again 400 DEG C insulation 6h obtain
The Preburning material of manganese silicate of lithium.Preburning material is carried out it is dry-mixed, continue in a nitrogen atmosphere raise temperature to 800 DEG C insulation 10h, you can
Obtain undoped, 2% carbon-coated lithium manganese silicate anode material Li2MnSiO4/C。
Embodiment 2：Example 2 in molar ratio:0.99:0.01:1 weighs raw material lithium nitrate, manganese acetate, magnesium nitrate and nano-silica
SiClx, adds dry-mixed after carbon source polyvinyl alcohol, and polyvinyl alcohol dosage is defined to final manganese silicate of lithium material surface carbon residue
Mass fraction is 3%.In a nitrogen atmosphere, by mixture 90 DEG C keep the temperature 2h, rise temperature to 250 DEG C insulation 2h, heat up again
The Preburning material of manganese silicate of lithium is obtained to 550 DEG C of insulation 1h.Preburning material is carried out it is dry-mixed, continue in a nitrogen atmosphere raise temperature extremely
780 DEG C of insulation 8h, you can obtain Mg doping, 3% carbon-coated lithium manganese silicate anode material Li2Mn0.99Mg0.01SiO4/C。
Embodiment 3：Example 2 in molar ratio:0.98:0.02:1 weighs raw material lithium hydroxide, manganese acetate, aluminum nitrate and nanometer two
Silica, adds dry-mixed after carbon source glucose, and glucose dosage is defined to the matter of final manganese silicate of lithium material surface carbon residue
It is 5% to measure fraction.In a nitrogen atmosphere, by mixture 120 DEG C keep the temperature 2h, rise temperature to 160 DEG C insulation 5h, be warming up to again
350 DEG C of insulation 8h obtain the Preburning material of manganese silicate of lithium.Preburning material is carried out it is dry-mixed, continue in a nitrogen atmosphere raise temperature extremely
850 DEG C of insulation 4h, you can obtain Al doping, 5% carbon-coated lithium manganese silicate anode material Li2Mn0.98Al0.02SiO4/C。
Embodiment 4：Example 2 in molar ratio:0.96:0.04:1 weighs raw material lithium nitrate, manganese acetate, zinc acetate and nano-silica
SiClx, adds dry-mixed after carbon source sucrose, and dosage of sucrose is defined to the mass fraction of final manganese silicate of lithium material surface carbon residue
For 15%.In a nitrogen atmosphere, by mixture 100 DEG C keep the temperature 4h, rise temperature to 190 DEG C insulation 8h, be warming up to 550 DEG C again
Insulation 5h obtains the Preburning material of manganese silicate of lithium.Preburning material is carried out it is dry-mixed, continue in a nitrogen atmosphere raise temperature to 650 DEG C guarantor
Warm 20h, you can obtain Zn doping, 15% carbon-coated lithium manganese silicate anode material Li2Mn0.96Zn0.04SiO4/C。
Embodiment 5：Example 2 in molar ratio:0.97:0.03:1 weighs raw material lithium nitrate, manganese acetate, copper acetate and nano-silica
SiClx, adds dry-mixed after carbon source polyvinyl alcohol, and polyvinyl alcohol dosage is defined to final manganese silicate of lithium material surface carbon residue
Mass fraction is 6%.In a nitrogen atmosphere, by mixture 90 DEG C keep the temperature 3h, rise temperature to 235 DEG C insulation 4h, heat up again
The Preburning material of manganese silicate of lithium is obtained to 450 DEG C of insulation 3h.Preburning material is carried out it is dry-mixed, continue in a nitrogen atmosphere raise temperature extremely
750 DEG C of insulation 10h, you can obtain Cu doping, 6% carbon-coated lithium manganese silicate anode material Li2Mn0.97Cu0.03SiO4/C。
Embodiment 6：Example 1 in molar ratio:0.85:0.15:1 weighs oxide spinel lithium, manganese acetate, cobalt acetate and nano-silica
SiClx, adds dry-mixed after carbon source glucose, and glucose dosage is defined to the quality of final manganese silicate of lithium material surface carbon residue
Fraction is 6.5%.In a nitrogen atmosphere, by mixture 150 DEG C keep the temperature 8h, rise temperature to 220 DEG C insulation 0.5h, heat up again
The Preburning material of manganese silicate of lithium is obtained to 500 DEG C of insulation 5h.Preburning material is carried out it is dry-mixed, continue in a nitrogen atmosphere raise temperature extremely
850 DEG C of insulation 12h, you can obtain Co doping, 6.5% carbon-coated lithium manganese silicate anode material Li2Mn0.85Co0.15SiO4/C。
Embodiment 7：Example 2 in molar ratio:0.93:0.05:0.02:1 weighs raw material lithium acetate, manganese acetate, cobalt acetate, acetic acid
Magnesium and nano silicon dioxide, add dry-mixed after carbon source sucrose, and it is residual that dosage of sucrose is defined to final manganese silicate of lithium material surface
The mass fraction of carbon is 5%.In a nitrogen atmosphere, mixture is kept the temperature to 4h, rise temperature to 200 DEG C of insulation 2h, again at 140 DEG C
It is warming up to 450 DEG C of insulation 6h and obtains the Preburning material of manganese silicate of lithium.Preburning material is carried out it is dry-mixed, continue in a nitrogen atmosphere rise temperature
Spend to 800 DEG C of insulation 12h, you can obtain Co, Mg codope, 5% carbon-coated lithium manganese silicate anode material Li2Mn0.93Co0.05Mg0.02SiO4/C。
Table 1 contrasts for the physical and chemical performance characterization of each embodiment.Wherein, specific discharge capacity is surveyed using 2016 button half-cells
Examination, is lithium piece to electrode, discharge and recharge section is 2.5-4.8V.As can be seen that manganese silicate of lithium powder electricity prepared by comparative example
Resistance rate highest, its electronic conductivity is minimum, and specific discharge capacity, high rate performance and capacity retention ratio are also minimum.In embodiment 1, adopt
With manganese acetate be manganese source and watery fusion, the performance of the manganese silicate of lithium material post-processed again are greatly improved：To the greatest extent
Pipe carbon content is reduced to 2%, its resistivity reduces electrical conductivity and improves, and gram volume brings up to 151.7mAh/g under 0.05C.Again into one
After step carries out cation doping, powder resistance rate further shows different degrees of decline, and the amplification ratio under different electric currents
Capacity all obtains a degree of lifting, and cycle performance is also improved.Wherein, compared with comparative example, carbon contains embodiment 7
Measure identical, but using manganese acetate raw material, after Mg and Co codopes, resistivity reduces nearly half, lower gram of appearance of 0.05C
Amount is increased by about one time, and high rate performance and cycle performance have obtained tremendous increase.This shows, uses manganese acetate as raw material,
Each component obtains more excellent mixed effect under molten condition；Using the cation dopings such as Mg, Al, Zn, Cu or Co, energy
The electronic conductivity of material is enough lifted, and is had a certain upgrade to the structural stability of manganese silicate of lithium.
The embodiments of the present invention described above are not intended to limit the scope of the present invention.It is any in the present invention
Spirit and principle within the modifications, equivalent substitutions and improvements made etc., should be included in the claim protection model of the present invention
Within enclosing.
Claims (6)
1. a kind of preparation method of lithium manganese silicate type positive electrode material of lithium ion battery, it is characterised in that the positive electrode
Chemical general formula is Li2Mn1-xMxSiO4/ C, wherein 0<X≤0.15, doping metals M are one kind or more in Mg, Al, Zn, Cu, Co
Kind, the content of surface coated carbon is 2%~15%；
Above-mentioned lithium manganese silicate type positive electrode material of lithium ion battery is prepared with the following method, specifically includes following steps：
(1) according to chemical formula Li2Mn1-xMxSiO4Lithium salts, manganese salt, doping M salt and silicon source are weighed in proportion, and it is laggard to add carbon source
Row is dry-mixed, obtains dry-blended mixture；
(2) dry-blended mixture obtained in step (1) is warming up to 80 DEG C~150 DEG C of temperature and keeps the temperature 0.5~8h, reach manganese salt
To molten condition and doping M salt and manganese salt congruent melting, and realize fully to infiltrate with other raw materials and mix；It is continuously heating to temperature 160
DEG C~250 DEG C and 0.5~8h of insulation, organic carbon source is reached molten condition, and fully infiltrate and mix with other raw materials；After of continuing rising
Temperature is to 350 DEG C~500 DEG C of temperature and keeps the temperature 1~8h, each raw material is fully reacted, obtains Preburning material；
(3) it is the Preburning material obtained in step (2) progress is dry-mixed, it is warming up to 650 DEG C~850 DEG C of temperature and keeps the temperature 4~20h, into
Row sintering reaction.
2. the preparation method of lithium manganese silicate type positive electrode material of lithium ion battery according to claim 1, it is characterised in that step
Suddenly one or more of the lithium salts in (1) in lithium acetate, lithium nitrate, lithium hydroxide and lithium carbonate.
3. the preparation method of lithium manganese silicate type positive electrode material of lithium ion battery according to claim 1, it is characterised in that step
Suddenly the manganese salt in (1) selects the manganese acetate of low melting point.
4. the preparation method of lithium manganese silicate type positive electrode material of lithium ion battery according to claim 1, it is characterised in that step
Suddenly one or more of the doped chemical M in (1) in Mg, Al, Zn, Cu, Co, M salt are selected in acetate and nitrate
It is one or more.
5. the preparation method of lithium manganese silicate type positive electrode material of lithium ion battery according to claim 1, it is characterised in that step
Suddenly the silicon source in (1) selects nano silicon dioxide.
6. the preparation method of lithium manganese silicate type positive electrode material of lithium ion battery according to claim 1, it is characterised in that institute
One or more of the carbon source stated in glucose, sucrose and polyvinyl alcohol, wherein, the matter of final product surface amorphous carbon
It is 2%~15% to measure fraction.
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| CN106784616B (en) * | 2016-12-06 | 2019-06-25 | 广州汽车集团股份有限公司 | The self-assembly preparation method thereof and positive electrode composition of spherical manganese silicate of lithium composite material |
| CN106848253A (en) * | 2017-03-20 | 2017-06-13 | 电子科技大学 | A kind of anode material for lithium-ion batteries Li2Mn1‑xMgxSiO4/ C and preparation method thereof |
| CN107359325A (en) * | 2017-06-22 | 2017-11-17 | 吉林大学 | The preparation method of carbon coating manganese silicate of lithium composite |
| CN107546386B (en) * | 2017-09-12 | 2020-04-07 | 中南大学 | Alkaline earth metal ion doped silicomanganese base lithium/carbon composite material and preparation method thereof |
| CN111017999B (en) * | 2019-12-13 | 2021-11-30 | 中国科学院山西煤炭化学研究所 | Molten salt three-step method for preparing lithium ion sieve precursor Li1.6Mn1.6O4And applications thereof |
| CN111689525B (en) * | 2020-05-27 | 2022-08-19 | 厦门厦钨新能源材料股份有限公司 | Preparation method of orthosilicate anode material coated ternary material |
| CN114122337A (en) * | 2020-08-28 | 2022-03-01 | 深圳市比亚迪锂电池有限公司 | Cathode material and preparation method thereof, lithium ion battery cathode and lithium ion battery |
| CN112467122B (en) * | 2020-12-03 | 2023-01-31 | 松山湖材料实验室 | Lithium orthosilicate composite material and preparation method and application thereof |
| CN113078308B (en) * | 2021-06-04 | 2021-08-24 | 蜂巢能源科技有限公司 | Cobalt-free and nickel-free positive electrode material, preparation method thereof and battery |
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