CN103311551A - Negative material of lithium-ion battery and preparation method thereof - Google Patents
Negative material of lithium-ion battery and preparation method thereof Download PDFInfo
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- CN103311551A CN103311551A CN2013102195264A CN201310219526A CN103311551A CN 103311551 A CN103311551 A CN 103311551A CN 2013102195264 A CN2013102195264 A CN 2013102195264A CN 201310219526 A CN201310219526 A CN 201310219526A CN 103311551 A CN103311551 A CN 103311551A
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- ion battery
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- lithium ion
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000010439 graphite Substances 0.000 claims abstract description 42
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 41
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 31
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 30
- 239000011247 coating layer Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010298 pulverizing process Methods 0.000 claims abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 23
- 239000008187 granular material Substances 0.000 claims description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000003610 charcoal Substances 0.000 claims description 14
- 230000008859 change Effects 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006136 alcoholysis reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 19
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 229920000049 Carbon (fiber) Polymers 0.000 abstract 1
- 239000004917 carbon fiber Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 230000002427 irreversible effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229910021382 natural graphite Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002931 mesocarbon microbead Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 206010023198 Joint ankylosis Diseases 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 240000003936 Plumbago auriculata Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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 relates to a negative material of a lithium-ion battery and a preparation method thereof, which belong to the field of a lithium battery. The negative material of the lithium-ion battery consists of graphite particles with coating layers, wherein each coating layer consists of 85 to 95 percent v/v of lithium carbonate and 5 to 15 percent v/v of carbon fibers. The preparation method of the negative material of the lithium-ion battery comprises the following steps of: a, mixing polyving akohol and lithium hydroxide to obtain a mixed solution; b, adding the graphite particles into the mixed solution to be stirred, and drying to obtain a dry material, wherein the weight ratio of the graphite particles to LiOH.H2O is (100-500): 1; c, adding inert gas into the dry material, and heating the dry material to be thermally insulated for 0.5h to 5h; d, introducing air, and continuously preserving the heat for 0.5h to 5h; and e, cooling, drying and pulverizing the material to obtain the negative material. The negative material of the lithium-ion battery has the advantages of good performance, simple preparation process and short preparation time.
Description
Technical field
The present invention relates to negative material of lithium ion battery and preparation method thereof, belong to the lithium battery field.
Background technology
As efficient secondary energy sources, lithium ion battery has been widely used on various portable type electronic products and the electric tool.Lithium ion battery generally adopts cobalt acid lithium (LiCoO at present
2) as positive electrode, graphite or MCMB are as negative material, lithium hexafluoro phosphate is dissolved in the solution of carbonic ester as electrolyte.
In general, to the basic demand of lithium ion battery negative material be: 1) higher lithium embedded quantity is arranged, to guarantee battery higher specific capacity is arranged, this requires material to have loose internal structure; 2) having electron conduction, also namely must be electric conducting material; 3) energy conducting Li atom can allow the Li atom more freely spread in inside; 4) embedding lithium current potential is as far as possible low, otherwise can reduce the discharge voltage of battery; 5) have higher structural stability, chemical stability and thermal stability; 6) price is as far as possible low; 7) use safety, nuisanceless pollution.
The carbon material that contains graphite-structure can satisfy above-mentioned requirements substantially.The graphite negative electrodes material comprises native graphite, Delanium and composite graphite three classes, is that 20～40 microns almost spherical particle forms by particle diameter generally.Here composite graphite refers to the compound of native graphite and Delanium, takes into account the characteristics of the two.Three kinds of phase class carbon microspheres in the middle of artificial plumbago negative pole material can be divided into again, needle coke class and petroleum coke classes; Phase class carbon microspheres in the middle of wherein mainly being, actual capacity is greater than 320mAh/g, and advantage is that granule regularizing, compacted density are high, and shortcoming is that cost is higher.The actual capacity of natural graphite negative electrode material is greater than 340mAh/g, and shortcoming is that particle irregularity, compacted density are slightly low, and advantage is that cost is low.Graphite material commonly used or the theoretical specific capacity of MCMB material are 372mAh/g at present, and actual specific capacity is generally at 330～350mAh/g, and cycle life can reach 1000 times.
When using as negative material, generally need to form " nucleocapsid structure " on the graphite granule surface in advance.Natural graphite particles generally contains impurity, is irregularly shaped, and specific area is large, and bulk density is little, and each particle reality is comprised of a lot of little crystal grain, therefore can not be directly as negative material.The method of processing is purification, spheroidization and coating successively, and wherein front two technology are very ripe, existing powdered graphite supply through purification and spheroidization on the market.Each natural graphite particles generally is comprised of a plurality of tiny crystal grain.The purpose of coated natural graphite particle is, allow in the particle the small grains tight agglomeration together, form so-called " nucleocapsid structure ", to avoiding intercrystalline cracking in charge and discharge process.The method that coats at present generally is, at first coat one deck carbon compound on the natural graphite particles surface, such as phenolic resins, carbamide resin, pitch, organic substance, macromolecular compound etc., and then high temperature carbonization obtain the approximately thick amorphous carbon of 60～150nm of one deck.The natural graphite negative electrode material that obtains so can perform well in preparing small-scale lithium ion cell.For the Delanium particle, for example MCMB also need to form similarly " nucleocapsid structure " at particle surface usually, to improving the electrochemistry cycle performance of negative material.
In the initial charge process of lithium ion battery, to reduce carbonic ester electrolyte at the newly-generated Li atom of graphite negative electrodes material surface, form the passivation layer that one deck is covered in the negative material surface.Its main component is lithium carbonate (Li
2CO
3).This passivation layer is a kind of boundary layer, and thickness is about 100～120nm, has the feature of solid electrolyte, is electronic body, but Li
+Excellence conductor.Li
+Can freely embed and deviate from negative pole via this passivation layer, so this passivation layer be called solid electrolyte interface film (Solid Electrolyte Interface), be called for short the SEI film.During initial charge, form the SEI film and will consume certain charge capacity, this is so that the Li that deviates from from positive pole
+In a part be used to form negative pole SEI film, this part Li
+Can not return in the discharge process afterwards in the positive electrode, cause thus the irreversible capacity loss of battery, generally can account for 20% of battery total capacity.How reducing this irreversible capacity loss, is one of research direction of lithium ion battery.The SEI film has stoped the further reaction of electrode material and electrolyte, has guaranteed the life-span of battery; In addition, the SEI film has also stoped solvent molecule to be embedded in the interlayer structure of graphite, has guaranteed the stable of negative pole crystal structure; Therefore, its existence is significant.The direction of research should be how to obtain the most effective SEI film with minimum cost.Usual way is to add some additives in electrolyte, so as with very little irreversible capacity loss as cost, form fine and close SEI film.
The patent that Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences delivered in 1999 " the preparation CN97115893.2 of lithium ion battery carbon material negative pole " adopts the inorganic or organic solution that contains lithium-ion electrolyte salt or its oxygenatedchemicals to process the graphite-like electrode of machine-shaping, generate in advance the SEI film of one deck densification at electrode surface, to improve first charge-discharge efficiency and the stable circulation capacity of silicon/carbon/graphite in lithium ion batteries class negative material.The electrolytic salt here comprises lithium carbonate, lithium hydroxide, lithia, lithium chloride etc.Technical process roughly is: 1) preparation graphite-like powder electrode, machine-shaping; 2) electrode is flooded in containing the solution of electrolytic salt; 3) at 100～200 ℃ of lower electrode vacuum dryings.It is said, the electrolytic thin-membrane of using the preparation of this patent of invention is large to the improvement amplitude of graphite-like electrode performance, Turbostratic carbon is also improved significantly.But its first charge-discharge efficiency also can only be controlled at 60～91%, and has preparation technology's shortcoming such as long consuming time.
Summary of the invention
The technical problem to be solved in the present invention is that negative material of a kind of lithium ion battery and preparation method thereof is provided.
The negative material of lithium ion battery of the present invention is the graphite granule with coating layer, and wherein, described coating layer is preferably fibrous by the charcoal of the lithium carbonate of 85～95%v/v and 5～15%v/v; More preferably fibrous by the charcoal of the lithium carbonate of 90%v/v and 10%v/v.
The lithium carbonate film has " nucleocapsid structure " by the graphite-like particle, can avoid intercrystalline cracking in charge and discharge process, the cycle life that has so just prolonged the graphite negative electrodes material; This lithium carbonate film also has the effect of SEI film on the other hand, also namely just has been pre-formed the SEI film on most surfaces of graphite negative electrodes before the battery initial charge, so just can effectively reduce irreversible capacity loss.
Further, the invention also discloses the preparation method of the negative material of lithium ion battery, comprise the steps:
A, polyvinyl alcohol and lithium hydroxide are mixed, obtain mixed solution; Wherein, described polyvinyl alcohol is preferably the high-molecular polyvinyl alcohol compound with any molecular weight; Polyvinyl alcohol/LiOHH
2The weight ratio of O is preferably 1.5～2.5:1
B, add graphite granule in mixed solution, stir, drying obtains dried material; Wherein, graphite granule/LiOHH
2The weight ratio of O is preferably 200～400:1;
C, pass into inert atmosphere in dried material, preferably be heated to 400～500 ℃, temperature retention time is preferably 0.5～5 hour; Wherein, described inert atmosphere be not with reaction system in the gas of material reaction, such as nitrogen, carbon dioxide, hydrogen, argon gas, helium etc.;
D, stop to pass into inert atmosphere, change and pass into air, continue insulation, temperature retention time is preferably 0.5～5 hour;
E, cooling, drying, pulverizing, and get final product.
Further, the alcoholysis degree of described polyvinyl alcohol is preferably greater than 50%.
Wherein, the c step is under high temperature and inert atmosphere protection, and carbonization reaction has occured polyvinyl alcohol, and reaction equation is as follows:
(CH
2CHOH)
n→C
2n+H
2O↑+H
2↑ （1）
Reaction obtains the lithium hydroxide film of charcoal fiber doping;
The d step allows carbon atom and oxygen reaction generate fine and close lithium carbonate film in lithium hydroxide, the film again in high temperature and air atmosphere, closely is attached to particle surface.Under 400～500 ℃ in air graphite surface have obvious oxidation, react, reaction equation is as follows:
C+O
2→CO
2 （2）
The product carbon dioxide again can with the lithium hydroxide generation lithium carbonate that reacts, reaction equation is as follows:
CO
2+2LiOH→Li
2CO
3+H
2O （3）
Because lithium carbonate generates in reaction system, therefore can be attached to more closely particle surface, form fine and close lithium carbonate film; Owing to containing a large amount of lithium ions in this film, should be the SEI film with good lithium ion ducting capacity therefore again.Therefore, the inventive method makes the negative material that obtains and has simultaneously " nucleocapsid structure " and " SEI film " double action concurrently.
Pure lithium carbonate coating layer does not have electron conduction, the graphite granule that coats behind the pure lithium carbonate will be difficult to use as negative material, the present invention adopts the charcoal fiber that obtains after the polyvinyl alcohol charing to be incorporated in the final lithium carbonate film, so just can provide electron conduction for the lithium carbonate coating layer.In coating layer, allow the volume of charcoal fiber only account for 5～15% of coating layer cumulative volume; Be equivalent to like this on the surface of graphite granule, have 85～95% surface to be covered by lithium carbonate, and only have 5～15% surface by the charcoal fiber-covered; That is to say, approximately 85～95% parts on graphite granule surface have formed the SEI film, and only have 5～15% surface to form the SEI film by electrolytic process when initial charge; Therefore, by coating technology of the present invention, can reduce the irreversible capacity loss more than 90%.
Beneficial effect of the present invention:
1, the cycle life of the negative material of lithium ion battery of the present invention is higher than common 1000 times level greater than 3000 times; Irreversible capacity loss is less than 2%, far below common approximately 10% level; Actual capacity is on close level with common greater than 340mAh/g.
2, the preparation method of the negative material of lithium ion battery of the present invention, technique is simple, it is 19 hours that ankylose becomes the time, the shortest only is 3.5 hours, compare number of patent application and be the preparation (preparation time is at least 204 hours) of 97115893.2 lithium ion battery carbon material negative pole, shortened widely preparation time.
3, raw material nonirritant, and among the whole preparation technology, do not have the three wastes to produce.
Embodiment
The negative material of lithium ion battery of the present invention is the graphite granule with coating layer, and wherein, described coating layer is preferably fibrous by the charcoal of the lithium carbonate of 85～95%v/v and 5～15%v/v; More preferably fibrous by the charcoal of the lithium carbonate of 90%v/v and 10%v/v.
The lithium carbonate film has " nucleocapsid structure " by the graphite-like particle, can avoid intercrystalline cracking in charge and discharge process, the cycle life that has so just prolonged the graphite negative electrodes material; This lithium carbonate film also has the effect of SEI film on the other hand, also namely just has been pre-formed the SEI film on most surfaces of graphite negative electrodes before the battery initial charge, so just can effectively reduce irreversible capacity loss.
Further, the invention also discloses the preparation method of the negative material of lithium ion battery, comprise the steps:
A, polyvinyl alcohol and lithium hydroxide are mixed, obtain mixed solution; Wherein, described polyvinyl alcohol is preferably the high-molecular polyvinyl alcohol compound with any molecular weight; Polyvinyl alcohol/LiOHH
2The weight ratio of O is preferably 1.5～2.5:1
B, add graphite granule in mixed solution, stir, drying obtains dried material; Wherein, graphite granule/LiOHH
2The weight ratio of O is preferably 200～400:1;
C, pass into inert atmosphere in dried material, preferably be heated to 400～500 ℃, temperature retention time is preferably 0.5～5 hour; Wherein, described inert atmosphere be not with reaction system in the gas of material reaction, such as nitrogen, carbon dioxide, hydrogen, argon gas, helium etc.;
D, stop to pass into inert atmosphere, change and pass into air, continue insulation, temperature retention time is preferably 0.5～5 hour;
E, cooling, drying, pulverizing, and get final product.
Further, the alcoholysis degree of described polyvinyl alcohol is preferably greater than 50%.
Wherein, the c step is under high temperature and inert atmosphere protection, and carbonization reaction has occured polyvinyl alcohol, and reaction equation is as follows:
(CH
2CHOH)
n→C
2n+H
2O↑+H
2↑ （1）
Reaction obtains the lithium hydroxide film of charcoal fiber doping;
The d step allows carbon atom and oxygen reaction generate fine and close lithium carbonate film in lithium hydroxide, the film again in high temperature and air atmosphere, closely is attached to particle surface.Under 400～500 ℃ in air graphite surface have obvious oxidation, react, reaction equation is as follows:
C+O
2→CO
2 （2）
The product carbon dioxide again can with the lithium hydroxide generation lithium carbonate that reacts, reaction equation is as follows:
CO
2+2LiOH→Li
2CO
3+H
2O （3）
Because lithium carbonate generates in reaction system, therefore can be attached to more closely particle surface, form fine and close lithium carbonate film; Owing to containing a large amount of lithium ions in this film, should be the SEI film with good lithium ion ducting capacity therefore again.Therefore, the inventive method makes the negative material that obtains and has simultaneously " nucleocapsid structure " and " SEI film " double action concurrently.
Pure lithium carbonate coating layer does not have electron conduction, the graphite granule that coats behind the pure lithium carbonate will be difficult to use as negative material, the present invention adopts the charcoal fiber that obtains after the polyvinyl alcohol charing to be incorporated in the final lithium carbonate film, so just can provide electron conduction for the lithium carbonate coating layer.In coating layer, allow the volume of charcoal fiber only account for 5～15% of coating layer cumulative volume; Be equivalent to like this on the surface of graphite granule, have 85～95% surface to be covered by lithium carbonate, and only have 5～15% surface by the charcoal fiber-covered; That is to say, approximately 85～95% parts on graphite granule surface have formed the SEI film, and only have 5～15% surface to form the SEI film by electrolytic process when initial charge; Therefore, by coating technology of the present invention, can reduce the irreversible capacity loss more than 90%.
Below in conjunction with embodiment the specific embodiment of the present invention is further described, does not therefore limit the present invention among the described scope of embodiments.
Embodiment 1 adopts the inventive method to prepare lithium ion battery negative material
A, polyvinyl alcohol and lithium hydroxide are mixed, obtain mixed solution; Wherein, polyvinyl alcohol/LiOHH
2The weight ratio of O is 1.5:1;
B, add graphite granule in mixed solution, stir, drying obtains dried material; Wherein, graphite granule/LiOHH
2The weight ratio of O is 200:1;
C, in dried material, pass into helium atmosphere, be heated to 400 ℃, be incubated 5 hours;
D, stop to pass into helium atmosphere, change and pass into air, continue insulation 5 hours;
E, cooling, drying, pulverizing, and get final product.
According to usual way, prepare negative material with this product, and be assembled into lithium ion battery, measure the chemical property of battery, after measured, the first capacity of preparation battery is 345mAh/g, irreversible capacity loss is 1.8% first, and circulating, the capability retention of battery is 84% after 3000 times.
The time of preparation lithium ion battery negative material is 13 hours altogether in the present embodiment.
Embodiment 2 adopts the inventive method to prepare lithium ion battery negative material
A, polyvinyl alcohol and lithium hydroxide are mixed, obtain mixed solution; Wherein, polyvinyl alcohol/LiOHH
2The weight ratio of O is 2:1;
B, add graphite granule in mixed solution, stir, drying obtains dried material; Wherein, graphite granule/LiOHH
2The weight ratio of O is 300:1;
C, in dried material, pass into hydrogen atmosphere, be heated to 450 ℃, be incubated 2 hours;
D, stop to pass into hydrogen atmosphere, change and pass into air, continue insulation 2 hours;
E, cooling, drying, pulverizing, and get final product.
According to usual way, prepare negative material with this product, and be assembled into lithium ion battery, measure the chemical property of battery, after measured, the first capacity of prepared battery is 347mAh/g, irreversible capacity loss is 1.7% first, and circulating, the capability retention of battery is 86% after 3000 times.
The time of preparation lithium ion battery negative material is 7 hours altogether in the present embodiment.
Embodiment 3 adopts the inventive method to prepare lithium ion battery negative material
A, polyvinyl alcohol and lithium hydroxide are mixed, obtain mixed solution; Wherein, polyvinyl alcohol/LiOHH
2The weight ratio of O is 2.5:1;
B, add graphite granule in mixed solution, stir, drying obtains dried material; Wherein, graphite granule/LiOHH
2The weight ratio of O is 400:1;
C, in dried material, pass into nitrogen atmosphere, be heated to 500 ℃, be incubated 0.5 hour;
D, stop to pass into nitrogen atmosphere, change and pass into air, continue insulation 0.5 hour;
E, cooling, drying, pulverizing, and get final product.
According to usual way, prepare negative material with this product, and be assembled into lithium ion battery, measure the chemical property of battery, after measured, the first capacity of prepared battery is 342mAh/g, irreversible capacity loss is 1.6% first, and circulating, the capability retention of battery is 82% after 3000 times.The time of preparation lithium ion battery negative material is 4 hours altogether in the present embodiment.
Claims (4)
1. the negative material of lithium ion battery, it is characterized in that: described negative material is the graphite granule with coating layer, wherein, described coating layer is fibrous by the charcoal of the lithium carbonate of 85～95%v/v and 5～15%v/v.
2. the negative material of lithium ion battery according to claim 1 is characterized in that: described coating layer is fibrous by the charcoal of the lithium carbonate of 90%v/v and 10%v/v.
3. the preparation method of the negative material of claim 1 or 2 described lithium ion batteries is characterized in that comprising the steps:
A, polyvinyl alcohol and lithium hydroxide are mixed, obtain mixed solution; Wherein, polyvinyl alcohol/LiOHH
2The weight ratio of O is 1.5～2.5:1;
B, add graphite granule in mixed solution, stir, drying obtains dried material; Wherein, graphite granule/LiOHH
2The weight ratio of O is 200～400:1;
C, in dried material, pass into inert atmosphere, be heated to 400～500 ℃, be incubated 0.5～5 hour; Wherein, described inert atmosphere be not with reaction system in the gas of material reaction;
D, stop to pass into inert atmosphere, change and pass into air, continue insulation 0.5～5 hour;
E, cooling, drying, pulverizing, and get final product.
4. the preparation method of the negative material of lithium ion battery according to claim 3, it is characterized in that: the alcoholysis degree of described polyvinyl alcohol is greater than 50%.
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| CN106611838A (en) * | 2015-10-27 | 2017-05-03 | 宁德新能源科技有限公司 | Modified negative electrode active material, negative electrode plate and secondary battery |
| CN106972166A (en) * | 2017-05-17 | 2017-07-21 | 江西南氏锂电新材料有限公司 | A kind of lithium ion battery negative material and preparation method thereof |
| CN108695492A (en) * | 2017-03-31 | 2018-10-23 | Tdk株式会社 | Lithium powder, lithium ion secondary battery cathode and lithium rechargeable battery |
| CN111584873A (en) * | 2020-05-26 | 2020-08-25 | 大连中比能源科技有限公司 | Modified graphite negative electrode material and preparation method and application thereof |
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| CN108695492A (en) * | 2017-03-31 | 2018-10-23 | Tdk株式会社 | Lithium powder, lithium ion secondary battery cathode and lithium rechargeable battery |
| CN106972166A (en) * | 2017-05-17 | 2017-07-21 | 江西南氏锂电新材料有限公司 | A kind of lithium ion battery negative material and preparation method thereof |
| CN111584873A (en) * | 2020-05-26 | 2020-08-25 | 大连中比能源科技有限公司 | Modified graphite negative electrode material and preparation method and application thereof |
| CN112018387A (en) * | 2020-09-04 | 2020-12-01 | 安徽宝尔斯清洁能源有限公司 | Preparation method of preformed film negative electrode material and lithium ion battery |
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