CN108428861B - Ferrous sulfide coated lithium-rich cathode material and preparation method thereof - Google Patents
Ferrous sulfide coated lithium-rich cathode material and preparation method thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 89
- 239000010406 cathode material Substances 0.000 title claims abstract description 78
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 99
- 238000003756 stirring Methods 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910010296 Li1.2Mn0.4Ni0.2Co0.2O2 Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910018371 Mn(COOCH3)2 Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 101150041213 FES1 gene Proteins 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 101100324822 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) fes-4 gene Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/366—Composites as layered products
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- 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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Abstract
The invention discloses a lithium-rich cathode material coated by ferrous sulfide, which comprises a lithium-rich cathode material and ferrous sulfide coated on the surface of the lithium-rich cathode material. According to the invention, the lithium-rich cathode material coated by ferrous sulfide is prepared through precipitation and calcination processes, and tests show that the specific discharge capacity reaches 191.1mAh/g after 80 times of circulation under the current of 1C (300mA/g), the capacity retention rate reaches 92.63%, and the capacity retention rate is higher than 72.35% of that of an uncoated sample. The preparation method is simple, the surface structure of the anode material is enhanced, the cycle performance of the anode material is improved, and the application prospect is wide.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a ferrous sulfide coated lithium-rich cathode material and a preparation method thereof.
Background
In recent years, with the rapid development of science and technology, people have an increased environmental awareness, the demand of mobile terminals and the field of electric automobiles for high-energy density batteries is increased, and the anode materials with large specific capacity and high working voltage are receiving more and more attention. LiCoO, a currently commercially available positive electrode material2、LiMn2O4、LiFePO4Compared with the ternary cathode material, the discharge specific capacity of the ternary cathode material is lower than 200mAh/g, and the lithium-rich material xLi2MnO3·(1-x)LiMO2Has the advantages of discharge specific capacity over 250mAh/g, high working voltage, low production cost, environmental protection and the like, and is expected to become a new generation of lithium ion battery anodeA material.
During charging of lithium-rich cathode materials, Li2MnO3Activation at high voltage, Li in crystal lattice2The irreversible O is removed along with the generation of oxygen vacancy, and the lithium-rich cathode material is converted from a layered structure to a spinel structure in the charging and discharging processes, so that the lithium-rich cathode material has poor cycle performance, and the application of the lithium-rich cathode material in practice is severely restricted.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a ferrous sulfide coated lithium-rich cathode material and a preparation method thereof, which have the advantages of improving the cycle performance, enhancing the surface structure and being simple in preparation method.
The invention provides a lithium-rich cathode material coated by ferrous sulfide, which comprises a lithium-rich cathode material and ferrous sulfide coated on the surface of the lithium-rich cathode material.
Preferably, the lithium-rich cathode material has the chemical formula of Li1.2Mn0.4Ni0.2Co0.2O2。
Preferably, the structure is layered alpha-NaFeO2A shaped structure, the layered space group being
Preferably, the mass percentage of the ferrous sulfide is 1-3% based on the ferrous sulfide coated lithium-rich cathode material.
The invention also provides a preparation method of the ferrous sulfide coated lithium-rich cathode material, which comprises the following steps:
s1, weighing FeSO according to the molar ratio of Fe to S being 1:1-1.24·7H2O and (NH)4)2S aqueous solution of FeSO4·7H2Dissolving O in deionized water to prepare solution A;
s2 (NH)4)2Dropping the aqueous solution of S into the solution A and continuously stirring, adding a lithium-rich anode material, heating to 65-95 ℃, sealing and stirring for 3.5-4.5h, standing for 11.5-12.5h, filtering, washing, drying and grinding to obtain a solution B;
s3, roasting the B at the temperature of 400-500 ℃ for 3.5-4.5h in a protective atmosphere to obtain the lithium-rich cathode material coated by the ferrous sulfide.
Preferably, the stirring speed in S2 is 200-300r/min, preferably 260 r/min.
Preferably, the lithium-rich cathode material in S2 is prepared by the following process:
a. LiCOOCH is weighed according to the molar ratio of Li to Mn to Ni to Co of 1.2-1.4:0.38-0.42:0.18-0.22:0.18-0.223·2H2O、Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH)3)2·4H2Dissolving O in deionized water to prepare a mixed salt solution C;
b. according to the proportion of citric acid: c, weighing citric acid with the molar ratio of the total metal ions in 3-3.5:1, and dissolving the citric acid in deionized water to prepare a citric acid aqueous solution;
c. dropwise adding citric acid water solution into the solution C, heating to 76-84 ℃, and stirring for 3-5h to obtain gel D;
d. drying D at 75-85 ℃ for 11.5-12.5h, pre-burning at 476-484 ℃ for 4.6-5.4h in air atmosphere, taking out and grinding to obtain F;
e. heating F to 896-904 ℃ in a muffle furnace, calcining for 11.6-12.4h to prepare Li1.2Mn0.4Ni0.2Co0.2O2(LMNCO for short) powder.
Preferably, in the washing process in S2, the washing process is repeated 3 times by sequentially performing centrifugal washing with deionized water and absolute ethyl alcohol.
Preferably, the protective atmosphere in S3 is high purity argon.
The invention has the beneficial effects that: by coating crystalline FeS on the surface of the lithium-rich anode, the specific discharge capacity of the coated sample reaches 191.1mAh/g after 80-time circulation under the current of 1C (300mA/g), the capacity retention rate is 92.63 percent and is far higher than 72.35 percent of the uncoated sample, and the circulation performance of the lithium-rich anode material is obviously improved.
FeS has a layered structure, high electrochemical activity and a stable structure, and the lithium-rich anode surface is coated with ferrous sulfide, and a Li-Fe-S solid electrolyte transition layer is formed between a material matrix and a ferrous sulfide layer after coating, so that the resistance value of charge transfer can be greatly reduced, and the rate capability of the material is improved; and the contact area of the matrix and the electrolyte can be effectively reduced, the dissolution of Mn is inhibited, and the electrochemical performance and the structural stability of the circulating process of the material are improved. The method has the advantages that the precipitation and the calcination are used as basic process steps, the preparation process of the precipitation method is simple, the operation is easy, the cost is low, the structural stability and the thermal stability of a coating interface can be further enhanced in the calcination process, the lithium-rich cathode material with the FeS coated on the surface is prepared, the electrochemical performance, the rate performance and the cycle performance are excellent, and the application prospect is wide.
Drawings
FIG. 1 is an XRD pattern of FeS-1 prepared in example 1, FeS-2 prepared in example 2, FeS-3 prepared in example 3 and pure lithium rich material (LMNCO) according to the present invention.
FIG. 2 is an SEM image of FeS-1 prepared in example 1, FeS-2 prepared in example 2, FeS-3 prepared in example 3 and pure lithium rich material (LMNCO) according to the present invention; wherein: (a) is LMNCO, (b) is FeS-1, (c) is FeS-2, (d) is FeS-3.
FIG. 3 is HRTEM images of (a) LMNCO, (b) FeS-2 samples, and (c) EDS images of FeS-2.
FIG. 4 is a graph of the cycling performance of FeS-1 prepared in example 1, FeS-2 prepared in example 2, FeS-3 prepared in example 3 and pure lithium rich material (LMNCO) according to the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A lithium-rich cathode material coated by ferrous sulfide comprises the lithium-rich cathode material and the ferrous sulfide coated on the surface of the lithium-rich cathode material, and the preparation method comprises the following steps:
s1, weighing FeSO according to the molar ratio of Fe to S being 1:14·7H2O and (NH)4)2S aqueous solution of FeSO4·7H2Dissolving O in deionized water to prepare solution A;
s2 (NH)4)2Dropping the S aqueous solution into the A while stirring, and mixing the lithium-rich cathode material and the ferrous sulfide bagThe mass ratio of the coating is 100: 1 adding a lithium-rich cathode material, heating to 80 ℃, hermetically stirring at a stirring speed of 260r/min for 4 hours, standing for 12 hours, filtering, washing, drying and grinding to obtain B;
and S3, roasting the B for 5 hours at 450 ℃ under high-purity argon to prepare a lithium-rich cathode material coated by 1 wt% of ferrous sulfide, and marking the lithium-rich cathode material as FeS-1.
The lithium-rich cathode material in S2 is prepared by the following preparation process:
a. LiCOOCH is weighed according to the molar ratio of Li to Mn to Ni to Co of 1.32:0.4:0.2:0.23·2H2O、 Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH)3)2·4H2Dissolving O in deionized water to prepare a mixed salt solution C;
b. according to the proportion of citric acid: c, weighing citric acid with the molar ratio of the total metal ions in 3:1, and dissolving the citric acid in deionized water to prepare a citric acid aqueous solution;
c. dropwise adding a citric acid aqueous solution into the solution C, heating to 80 ℃, and stirring for 4 hours to obtain a gel D;
d. drying D at the temperature of 80 ℃ for 12h, pre-burning the D at the temperature of 480 ℃ for 5h in an air atmosphere, taking out and grinding the D to obtain E;
e. heating the E in a muffle furnace to 900 ℃, and calcining for 12h to obtain Li1.2Mn0.4Ni0.2Co0.2O2Powder;
example 2
A lithium-rich cathode material coated by ferrous sulfide comprises the lithium-rich cathode material and the ferrous sulfide coated on the surface of the lithium-rich cathode material, and the preparation method comprises the following steps:
s1, weighing FeSO according to the molar ratio of Fe to S being 1:14·7H2O and (NH)4)2S aqueous solution of FeSO4·7H2Dissolving O in deionized water to prepare solution A;
s2 (NH)4)2And (3) slowly dropping the S aqueous solution into the A and continuously stirring, wherein the mass ratio of the lithium-rich cathode material to the ferrous sulfide coating is 100: 2 adding lithium-rich cathode material, heating to 80 ℃, stirring at 260r/minStirring at a stirring speed for 4h in a sealing way, standing for 12h, filtering, washing, drying and grinding to obtain B;
and S3, roasting the B for 5 hours at 450 ℃ under high-purity argon to obtain the lithium-rich cathode material coated by 2 wt% of ferrous sulfide, and marking the lithium-rich cathode material as FeS-2.
The lithium-rich cathode material in S2 is prepared by the following preparation process:
a. LiCOOCH is weighed according to the molar ratio of Li to Mn to Ni to Co of 1.32:0.4:0.2:0.23·2H2O、 Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH)3)2·4H2Dissolving O in deionized water to prepare a mixed salt solution C;
b. according to the proportion of citric acid: c, weighing citric acid with the molar ratio of the total metal ions in 3:1, and dissolving the citric acid in deionized water to prepare a citric acid aqueous solution;
c. dropwise adding a citric acid aqueous solution into the solution C, heating to 80 ℃, and stirring for 4 hours to obtain a gel D;
d. drying D at the temperature of 80 ℃ for 12h, pre-burning the D at the temperature of 480 ℃ for 5h in an air atmosphere, taking out and grinding the D to obtain E;
e. heating the E in a muffle furnace to 900 ℃, and calcining for 12h to obtain Li1.2Mn0.4Ni0.2Co0.2O2Powder;
example 3
A lithium-rich cathode material coated by ferrous sulfide comprises the lithium-rich cathode material and the ferrous sulfide coated on the surface of the lithium-rich cathode material, and the preparation method comprises the following steps:
s1, weighing FeSO according to the molar ratio of Fe to S being 1:14·7H2O and (NH)4)2S aqueous solution of FeSO4·7H2Dissolving O in deionized water to prepare solution A;
s2 (NH)4)2And (3) dropping the S aqueous solution into the A and continuously stirring, wherein the mass ratio of the lithium-rich cathode material to the ferrous sulfide coating is 100: 3 adding a lithium-rich cathode material, heating to 80 ℃, hermetically stirring at a stirring speed of 260r/min for 4 hours, standing for 12 hours, filtering, washing, drying and grinding to obtain B;
and S3, roasting the B for 4 hours at 450 ℃ under high-purity argon to prepare a lithium-rich cathode material coated by ferrous sulfide with the weight percentage of 3 wt%, and marking the lithium-rich cathode material as FeS-3.
The lithium-rich cathode material in S2 is prepared by the following preparation process:
a. LiCOOCH is weighed according to the molar ratio of Li to Mn to Ni to Co of 1.32:0.4:0.2:0.23·2H2O、 Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH)3)2·4H2Dissolving O in deionized water to prepare a mixed salt solution C;
b. according to the proportion of citric acid: c, weighing citric acid with the molar ratio of the total metal ions in 3:1, and dissolving the citric acid in deionized water to prepare a citric acid aqueous solution;
c. dropwise adding a citric acid aqueous solution into the solution C, heating to 80 ℃, and stirring for 4 hours to obtain a gel D;
d. drying D at the temperature of 80 ℃ for 12h, pre-burning the D at the temperature of 480 ℃ for 5h in an air atmosphere, taking out and grinding the D to obtain E;
e. heating the E in a muffle furnace to 900 ℃, and calcining for 12h to obtain Li1.2Mn0.4Ni0.2Co0.2O2Powder;
example 4
A lithium-rich cathode material coated by ferrous sulfide comprises the lithium-rich cathode material and the ferrous sulfide coated on the surface of the lithium-rich cathode material, and the preparation method comprises the following steps:
s1, weighing FeSO according to the molar ratio of Fe to S being 1:1.24·7H2O and (NH)4)2S aqueous solution of FeSO4·7H2Dissolving O in deionized water to prepare solution A;
s2 (NH)4)2And (3) slowly dropping the S aqueous solution into the A and continuously stirring, wherein the mass ratio of the lithium-rich cathode material to the ferrous sulfide coating is 100: 2.5 adding a lithium-rich cathode material, heating to 95 ℃, hermetically stirring at a stirring speed of 200r/min for 3.5h, standing for 11.5h, filtering, washing, drying and grinding to obtain B;
and S3, roasting the B for 3.5 hours at 500 ℃ under high-purity argon to obtain the lithium-rich cathode material coated by the ferrous sulfide with the weight percent of 2.5, and marking the lithium-rich cathode material as FeS-4.
The lithium-rich cathode material in S2 is prepared by the following preparation process:
a. LiCOOCH is weighed according to the molar ratio of Li to Mn to Ni to Co of 1.4:0.38:0.18:0.183·2H2O、 Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH)3)2·4H2Dissolving O in deionized water to prepare a mixed salt solution C;
b. according to the proportion of citric acid: c, weighing citric acid with the molar ratio of the total metal ions in 3.5:1, and dissolving the citric acid in deionized water to prepare a citric acid aqueous solution;
c. dropwise adding a citric acid aqueous solution into the solution C, heating to 84 ℃, and stirring for 3h to obtain a gel D;
d. drying D at 85 ℃ for 11.5h, pre-burning at 485 ℃ for 4.6h in the air atmosphere, taking out and grinding to obtain E;
e. heating the E in a muffle furnace to 904 ℃, and calcining for 12.4h to obtain Li1.2Mn0.4Ni0.2Co0.2O2Powder;
example 5
A lithium-rich cathode material coated by ferrous sulfide comprises the lithium-rich cathode material and the ferrous sulfide coated on the surface of the lithium-rich cathode material, and the preparation method comprises the following steps:
s1, weighing FeSO according to the molar ratio of Fe to S being 1:1.14·7H2O and (NH)4)2S aqueous solution of FeSO4·7H2Dissolving O in deionized water to prepare solution A;
s2 (NH)4)2And (3) dropping the S aqueous solution into the A and continuously stirring, wherein the mass ratio of the lithium-rich cathode material to the ferrous sulfide coating is 100: 1.5 adding a lithium-rich cathode material, heating to 65 ℃, hermetically stirring at a stirring speed of 200r/min for 4.5h, standing for 12.5h, filtering, washing, drying and grinding to obtain B;
and S3, roasting the B for 4.5 hours at 400 ℃ under high-purity argon to obtain the lithium-rich cathode material coated by 1.5 wt% of ferrous sulfide, and marking the lithium-rich cathode material as FeS-5.
The lithium-rich cathode material in S2 is prepared by the following preparation process:
a. LiCOOCH is weighed according to the molar ratio of Li to Mn to Ni to Co of 1.2:0.42:0.22:0.223·2H2O、 Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH)3)2·4H2Dissolving O in deionized water to prepare a mixed salt solution C;
b. according to the proportion of citric acid: c, weighing citric acid with the molar ratio of the total metal ions in 3.3:1, and dissolving the citric acid in deionized water to prepare a citric acid aqueous solution;
c. dropwise adding a citric acid aqueous solution into the solution C, heating to 76 ℃, and stirring for 5 hours to obtain a gel D;
d. drying D at 70 deg.C for 12.5h, pre-baking at 476 deg.C in air atmosphere for 5.4h, taking out, and grinding to obtain E;
e. heating the E in a muffle furnace to 896 ℃, and calcining for 12.4h to obtain Li1.2Mn0.4Ni0.2Co0.2O2Powder;
XRD, SEM and TEM results of the pure lithium-rich material LMNCO, the FeS-1 prepared in the example 1, the FeS-2 prepared in the example 2 and the FeS-3 prepared in the example 3 are respectively shown in figures 1, 2 and 3, and test results show that the prepared ferrous sulfide is uniformly coated on the surface of the lithium-rich cathode material LMNCO and has uniform appearance. Adopting a 2032 coin cell to carry out electrochemical performance test, and according to the active materials: carbon black: dissolving poly (vinylidene fluoride) in N-methyl pyrrolidone at a mass ratio of 75:15:10, uniformly coating the poly (vinylidene fluoride) on an aluminum foil, drying at 120 ℃ for 24 hours to prepare a positive plate, taking a lithium plate as a negative electrode, taking Celgard 2400 as a diaphragm, taking 1M LiPF6 as an electrolyte, dissolving the lithium plate in EC/DMC/DEC (1:1:1in wt.%), completing the assembly process of the battery in a glove box, and carrying out the charge-discharge test of the battery on Xinwei CT-3008. As shown in fig. 4, it can be seen that, when the number of cycles is the same, the specific discharge capacity and capacity retention rate of the coated lithium-rich cathode material are higher than those of the uncoated lithium-rich cathode material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. A lithium-rich cathode material coated by ferrous sulfide is characterized by comprising a lithium-rich cathode material and ferrous sulfide coated on the surface of the lithium-rich cathode material, wherein a Li-Fe-S solid electrolyte transition layer is formed between a material matrix and a ferrous sulfide layer after coating;
the preparation method of the ferrous sulfide coated lithium-rich cathode material comprises the following steps:
s1, weighing FeSO according to the molar ratio of Fe to S =1:1-1.24·7H2O and (NH)4）2S aqueous solution of FeSO4·7H2Dissolving O in deionized water to prepare solution A;
s2 (NH)4）2Dropping the aqueous solution of S into the solution A and continuously stirring, adding a lithium-rich anode material, heating to 65-95 ℃, sealing and stirring for 3.5-4.5h, standing for 11.5-12.5h, filtering, washing, drying and grinding to obtain a solution B;
s3, roasting the B for 3.5-4.5h at the temperature of 500 ℃ in a protective atmosphere of 400-;
the lithium-rich cathode material in S2 is prepared by the following process:
a. LiCOOCH is weighed according to the molar ratio of Li to Mn to Ni to Co of 1.2-1.4:0.38-0.42:0.18-0.22:0.18-0.223·2H2O、Mn(COOCH3)2、Ni(COOCH3)2·4H2O and Co (COOCH)3)2·4H2Dissolving O in deionized water to prepare a mixed salt solution C;
b. according to the proportion of citric acid: c, weighing citric acid with the molar ratio of the total metal ions in 3-3.5:1, and dissolving the citric acid in deionized water to prepare a citric acid aqueous solution;
c. dropwise adding citric acid water solution into the solution C, heating to 76-84 ℃, and stirring for 3-5h to obtain gel D;
d. drying D at 75-85 ℃ for 11.5-12.5h, pre-burning at 476-484 ℃ for 4.6-5.4h in air atmosphere, taking out and grinding to obtain F;
e. heating F to 896-904 ℃ in a muffle furnace, calcining for 11.6-12.4h to prepare Li1.2Mn0.4Ni0.2Co0.2O2And (3) powder.
2. The ferrous sulfide coated lithium-rich cathode material as claimed in claim 1, wherein the lithium-rich cathode material has a chemical formula of Li1.2Mn0.4Ni0.2Co0.2O2。
3. The ferrous sulfide coated lithium-rich cathode material as claimed in claim 1, wherein the ferrous sulfide is 1-3% by weight of the ferrous sulfide coated lithium-rich cathode material.
4. The ferrous sulfide coated lithium-rich cathode material as claimed in claim 1, wherein the stirring speed in S2 is 200-300 r/min.
5. The ferrous sulfide coated lithium-rich cathode material as claimed in claim 1, wherein in the washing process in S2, deionized water and absolute ethyl alcohol are sequentially used for centrifugal washing, and the washing is repeated for 3 times.
6. The ferrous sulfide coated lithium-rich cathode material as claimed in claim 1, wherein the protective atmosphere in S3 is high purity argon.
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