CN101841019A - Carbon cladding layer expansion graphite composite material used for lithium ion batteries and preparation method thereof - Google Patents
Carbon cladding layer expansion graphite composite material used for lithium ion batteries and preparation method thereof Download PDFInfo
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Abstract
The invention provides a carbon cladding layer expansion graphite composite material used for lithium ion batteries and a preparation method thereof. The carbon cladding layer expansion graphite composite material has a shell-kernel structure, wherein, the inner kernel is phosphorus-doped layer expansion graphite, and the layer spacing is 0.3360-0.3390nm; the outer shell is a pyrolysis product of phenolic resin; the carbon cladding layer expansion graphite composite material is prepared by the processes of raw material pretreatment, oxidized intercalation, cladding and layer removing; phosphoric acid dissolved with organic acid or a phosphate-nitrate system is adopted as oxidized intercalator. Lithium ion battery cathode prepared by the carbon cladding layer expansion graphite composite material of the invention has the characteristics of high capacity, high power and long service life. The preparation method of the invention has the characteristics of simple and easily operated process, and moderate and practical conditions and the like.
Description
Technical field
The present invention relates to a kind of graphite-base composite material and preparation method, particularly lithium ion battery carbon cladding layer expansion graphite composite negative pole material and preparation method.
Background technology
Present business-like lithium ion battery adopts the graphite-like negative material mostly, though the graphite cathode material of this quasi-tradition has low and current potential platform and better cycle performance stably, but because its doff lithium capacity low (372mAh/g), and lithium ion is little by (1 * 10 at the diffusion coefficient of graphite layers
-12Cm/s), seriously restricting the raising of lithium ion battery specific power, specific capacity.
The interlamellar spacing that rationally increases graphite material is expected to fundamentally improve the specific capacity and the high rate performance of graphite-based negative material.Expanded graphite is the product with graphite raw material gained behind treatment steps such as oxidation, intercalation, expansion, has the mixed and disorderly characteristics that distribute from nanoscale to micron-sized interlamellar spacing.Expanded graphite as lithium ion battery negative material, can be improved the specific capacity of material on the one hand, can also improve the high rate performance of electrode on the other hand.Based on this, expanded graphite and modified expanded graphite negative material are admitted by people just gradually and might be become lithium ion battery negative material of new generation.
The Zou Lin of Tsing-Hua University-Kang Fei space seminars etc. are raw material with the spherical graphite, with H
2SO
4-H
2O
2Be the oxidation intercalator, make the resin charcoal by oxidation-expansion-coating processing and coat the microdilatancy graphite cathode material, its reversible capacity is 378mAh/g, capability retention through 100 circulating electrodes is 100% (Lin Zou, Feiyu Kang et al., Electrochimica Acta, 2009:54:3930-3934.).The Song Huaihe of Peking University etc. also is raw material with the MCMB, with H
2SO
4-KMnO
4For having prepared asphalt carbon, the oxidation intercalator coats expansion MCMB negative material, its reversible capacity is 260mAh/g, this material capability retention after 50 circulations is 100% (Shubin Yang, Huaihe Song, Xiaohong Chen.Electrochemistry Communications 2006; 8:137-42.).
Though present modified expanded graphite has excellent cycle performance and high rate performance preferably, but its specific capacity is not greatly improved, and illustrates that this type of actual storage lithium space with mixed and disorderly expanded graphite that distributes from nanoscale to micron-sized interlamellar spacing increases seldom.Moreover, owing in preparation process, introduced H
2SO
4, the sulphur composition is difficult to eliminate in the dusty material of gained, and the existence of residual sulfur is unfavorable for the electrochemical stability of material.In addition, all adopt the processing mode that expands and afterwards coat earlier in the bibliographical information, this process heat is handled very violent, destruction to subsphaeroidal graphite is serious, energy consumption is higher, and flow process is loaded down with trivial details, manufacturing cycle is longer, and these factors all are unfavorable for the commercial application of lithium ion battery with the modified expanded graphite negative material.
Summary of the invention
The present invention aims to provide a kind of carbon cladding layer expansion graphite composite negative pole material of lithium ion battery with high power capacity, high power, long-life characteristics, provides also simultaneously that a kind of preparation is simple, the method for mild condition practicality.
The present invention realizes by following scheme.
The lithium ion battery carbon cladding layer expansion graphite composite material, having " shell-nuclear " is that shell encases inner core, and kernel is the layer expansion graphite of Doping Phosphorus, and shell is the thermal decomposition product of phenolic resins.
Be specific capacity and the specific power of improving negative material, the interlamellar spacing d002 value of layer expansion graphite increases to 0.3360～0.3390nm.
Prepare the method for above-mentioned lithium ion battery, may further comprise the steps with the carbon cladding layer expansion graphite composite negative pole material:
The first step: oxidation intercalation operation, under-10～20 ℃ of conditions, in the graphite raw material system that to impregnated in solvent be organic acid phosphoric acid or its hydrogeneous salt with nitrate mixes, dip time is 1～24h, filtering and washing to filtrate pH value is 3～5, obtains required compound between graphite layers filter cake.The mass ratio of each composition is as follows: graphite: (phosphoric acid or salt): the nitrate mass ratio is 1: (2.0～4.5): (0.5～1.5), graphite: organic acid is 1: (1～20).Described phosphoric acid salt (comprising: monobasic phosphate or binary phosphate) is selected from a kind of in the following salt: ammonium salt, sylvite, sodium salt, and as NH
4H
2PO
4, K
2HPO
4, NaH
2PO
4Deng; Described nitrate is selected from a kind of in the following salt: ammonium salt, sylvite, sodium salt; Graphite raw material can adopt high-purity subsphaeroidal graphite-like materials such as the natural flake graphite after the purified shaping, natural micro crystal graphite, Delanium, and organic acid then can use organic acids commonly used such as oxalic acid, acetate, formic acid.
Second step: coating-delamination operation, the prepared compound between graphite layers filter cake of the first step is joined in the phenolic resins organic solution, after mixing, after curing, heat treatment, make the carbon cladding layer expansion graphite material; Formation and the phenolic resin carbon of having finished layer expansion graphite by a step heat treatment process simultaneously coat, and described heat-treat condition is as follows, and heating rate is 0.5～2 ℃/min; The atmosphere of selecting for use is the mixed atmosphere of nitrogen or nitrogen and hydrogen; Heat treatment temperature is 800～1000 ℃; Constant temperature time is 10～30min.Be (10～16) in graphite raw material and resin quality ratio: 1 ratio is used phenolic resins organic solution; Phenolic resins organic solution solvent for use is an absolute ethyl alcohol, and its concentration is 150～220g/ml; The resin solidification temperature is 100～150 ℃, and be 1～4h curing time.
In order to reduce the sulfur content in the graphite raw material; improve the chemical property of negative material; before described oxidation intercalation operation; need to increase the graphite raw material pretreatment process; detailed process is: under protective atmosphere; pending graphite raw material is heated to 900～1350 ℃, more than constant temperature heat treatment 0.5～3h, makes pretreated graphite raw material.The lower-cost nitrogen of the general employing of protective atmosphere also can use other inert gas certainly.
Before institute's prepared material is used for lithium ion battery, also need it again through subsequent treatment such as grinding, sieve, the particle size of final products should satisfy D50 in 20～25 mu m ranges, the largest particles is lower than 38 μ m.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention enlarges graphite layers by " oxidation intercalation-coating-delamination " technology apart from suitable, make the carbon cladding layer expansion graphite composite negative pole material, not only can significantly improve the embedding lithium space of material, increase the electrode reversible specific capacity, can also expand the diffusion admittance of lithium ion in graphite linings, improve the electrode high power performance.The present invention relates to the carbon cladding layer expansion graphite composite negative pole material and carry out the constant current charge-discharge test under the multiplying power of 0.15C, find that its reversible capacity can reach 430.5mAh/g, even under the 10C situation, this material also has higher specific capacity.
2. the present invention makes the carbon cladding layer expansion graphite composite negative pole material by " oxidation intercalation-coating-delamination ", has improved the cycle performance of layer expansion graphite material.0.15C 500 circulations of experience under the multiplying power, the capability retention of graphite electrode material of the present invention on average can reach more than 85%, meets the commercialization requirement of lithium ion battery fully.
3. dense H is not used in the used oxidized inserting layer agent of preparation method of the present invention
2SO
4Solution, and graphite raw material taked pretreating process, the sulfur content of the final dusty material of gained is lower than 80ppm, can effectively improve the chemical property of material.
4. preparation method of the present invention is with H
3PO
4Or its esters is intercalator, and this material at high temperature can at first dewater and become P
2O
5, then then reacting again and form with covalent bonds and mix phosphorus graphite with carbocyclic ring with carbon, the doping of phosphorus not only can promote the increase of graphite layers distance, can also strengthen layer expansion graphite interlaminar action power, makes more stable that its structure becomes.
5. preparation method of the present invention is the intercalation assistant with the organic acid, not only can strengthen H
3PO
4Or the intercalation effect of its esters, and the quantitative adding of organic acid can also be regulated the size of layer expansion graphite interlamellar spacing.
6. Technology for Heating Processing of the present invention is comparatively gentle, can effectively suppress the phenomenon that material increases severely because of the expansion specific area, in addition, formation and the charcoal of having finished layer expansion graphite by a step heat treatment process simultaneously coat, reduced the preparation technology of carbon cladding layer expansion graphite composite material greatly, it is very favourable that this prepares this negative material to industrialization.
Embodiment
Embodiment 1
Lithium ion battery carbon cladding layer expansion graphite composite negative pole material has " shell-nuclear " structure, and kernel is the layer expansion graphite of Doping Phosphorus, and shell is the thermal decomposition product of phenolic resins, and the graphite layers distance is 0.3387nm.
The preparation method of above-mentioned carbon cladding layer expansion graphite composite negative pole material is as follows:
The first step: at N
2Under the atmosphere protection, the micro crystal graphite raw material is heated to 1000 ℃, constant temperature heat treatment 0.5h gets preliminary treatment micro crystal graphite raw material after the cooling.
Second step: under-10 ℃ of temperature, with the pretreated micro crystal graphite raw material of 10g, 10gNaNO
3Joining the 20.0ml mass concentration with 20g oxalic acid is 85% dense H
3PO
4In the solution, leave standstill 12h after stirring, graphite: H
3PO
4: NaNO
3Mass ratio is 1: 3.37: 1, graphite: the oxalic acid mass ratio is 1: 2; Then above-mentioned viscous paste being washed to the pH value is 4, obtains the compound between graphite layers filter cake behind the vacuum filtration.
The 3rd step: gained compound between graphite layers filter cake is added in the ethanolic solution that is dissolved with 0.95g phenolic resins, phenol resin solution concentration is 200g/ml, and graphite raw material and phenolic resins mass ratio are 10.5: 1, after stirring, in 120 ℃ of curing 2h, then at N
2Under the atmosphere, be heated to 900 ℃ with the programming rate of 0.5 ℃/min, constant temperature 20min is cooled to room temperature afterwards, the gained meal is ground the back again and crosses 325 mesh standard sieves and make the smart powder of carbon cladding layer expansion graphite composite negative pole material.
Embodiment 2
Lithium ion battery carbon cladding layer expansion graphite composite negative pole material has " shell-nuclear " structure, and kernel is the layer expansion graphite of Doping Phosphorus, and shell is the thermal decomposition product of phenolic resins, and the graphite layers distance is 0.3383nm.
The preparation method of above-mentioned carbon cladding layer expansion graphite composite negative pole material is as follows:
The first step: at N
2Under the atmosphere protection, crystallite is heated to 1000 ℃, constant temperature heat treatment 2h gets preliminary treatment micro crystal graphite raw material after the cooling.
Second step: under 20 ℃ of temperature, with the pretreated micro crystal graphite raw material of 10g, 15gNaNO
3Join the NH that 80.0ml concentration is 300g/l successively with 50g acetate
4H
2PO
4In the solution, leave standstill 10h after stirring, graphite: NH
4H
2PO
4: NaNO
3Mass ratio is 1: 2.4: 1.5, graphite: the quality of acetic acid ratio is 1: 5. Then above-mentioned viscous paste being washed to the pH value is 5, obtains the compound between graphite layers filter cake behind the vacuum filtration.
The 3rd step: gained compound between graphite layers filter cake is added in the ethanolic solution that is dissolved with 0.95g phenolic resins, phenol resin solution concentration is 200g/ml, graphite raw material and phenolic resins mass ratio are about 10.5: 1, after stirring, solidify 3h in 120 ℃, then under nitrogen and the mixed atmosphere of hydrogen, programming rate with 1.5 ℃/min is heated to 800 ℃, constant temperature 30min, be cooled to room temperature afterwards, cross 325 mesh standard sieves after again the gained meal being ground and make the smart powder of carbon cladding layer expansion graphite composite negative pole material.
Embodiment 3
The smart powder of above-mentioned carbon cladding layer expansion graphite composite negative pole material is made into electrode; As a comparison, micro crystal graphite is ground, after 325 mesh sieves, gained-325 order graphite powder is become electrode, this is a comparative example 1.Other test condition is identical, test result such as following table:
Comparing result shows, the interlamellar spacing of carbon cladding layer expansion graphite composite negative pole material of the present invention is a bit larger tham the micro crystal graphite material, discharges and recharges chemical properties such as reversible specific capacity under the condition, cycle life with the lithium ion battery negative of its making at 0.15C, 10C and is improved largely.
Embodiment 4
Lithium ion battery carbon cladding layer expansion graphite composite negative pole material has " shell-nuclear " structure, and kernel is the layer expansion graphite of Doping Phosphorus, and shell is the thermal decomposition product of phenolic resins, and the graphite layers distance is 0.3390nm.
The preparation method of above-mentioned carbon cladding layer expansion graphite composite negative pole material is as follows:
The first step: at N
2Under the atmosphere protection, the Delanium raw material is heated to 1350 ℃, constant temperature heat treatment 1h gets preliminary treatment Delanium raw material after the cooling.
Second step: under 0 ℃ of temperature, with the pretreated Delanium raw material of 10g, 5gKNO
3Join the dense H of 20.0ml successively with 20g oxalic acid
3PO
4In the solution, leave standstill 5h after stirring, graphite: H
3PO
4: KNO
3Mass ratio is 1: 3.37: 0.5, graphite: the oxalic acid mass ratio is 1: 2; Then above-mentioned viscous paste being washed to the pH value is 3, obtains the compound between graphite layers filter cake behind the vacuum filtration.
The 3rd step: gained compound between graphite layers filter cake is added in the ethanolic solution that is dissolved with 0.7g phenolic resins, and phenol resin solution concentration is 220g/ml, and graphite raw material and phenolic resins mass ratio are about 14: 1, after stirring, in 150 ℃ of curing 3h, then at N
2Under the atmosphere, be heated to 1000 ℃ with the programming rate of 1 ℃/min, constant temperature 10min is cooled to room temperature afterwards, the gained meal is ground the back again and crosses 325 mesh standard sieves and make the smart powder of carbon cladding layer expansion graphite composite negative pole material.
Embodiment 5
The smart powder of above-mentioned carbon cladding layer expansion graphite composite negative pole material is made into electrode; As a comparison, Delanium is ground, after 325 mesh sieves, gained-325 order graphite powder is become electrode, this is a comparative example 2.Other test condition is identical, test result such as following table:
Comparing result shows, the interlamellar spacing of carbon cladding layer expansion graphite composite negative pole material of the present invention is a bit larger tham the Delanium material, discharges and recharges chemical properties such as reversible specific capacity under the condition, cycle life with the lithium ion battery negative of its making at 0.15C, 10C and is greatly improved.
Embodiment 6
Lithium ion battery carbon cladding layer expansion graphite composite negative pole material has " shell-nuclear " structure, and kernel is the layer expansion graphite of Doping Phosphorus, and shell is the thermal decomposition product of phenolic resins, and the graphite layers distance is 0.3364nm.
The preparation method of above-mentioned carbon cladding layer expansion graphite composite negative pole material is as follows:
The first step: at N
2Under the atmosphere protection, the crystalline flake graphite graphite raw material is heated to 900 ℃, constant temperature heat treatment 2h gets preliminary treatment crystalline flake graphite raw material after the cooling.
Second step: under 10 ℃ of temperature, with the pretreated crystalline flake graphite raw material of 10g, 10gNH
4NO
3Joining 26.3ml concentration successively with 10g acetate is 85% dense H
3PO
4In the solution, leave standstill 1h after stirring, graphite: H
3PO
4: NaNO
3Mass ratio is 1: 4.43: 1, graphite: the quality of acetic acid ratio is 1: 1.Then above-mentioned viscous paste being washed to the pH value is 5, obtains the compound between graphite layers filter cake behind the vacuum filtration.
The 3rd step: gained compound between graphite layers filter cake is added in the ethanolic solution that is dissolved with 0.63g phenolic resins, phenol resin solution concentration is 180g/ml, graphite raw material and phenolic resins mass ratio are about 16: 1, after stirring, solidify 2h in 150 ℃, then under nitrogen and the mixed atmosphere of hydrogen, programming rate with 2 ℃/min is heated to 800 ℃, constant temperature 30min, be cooled to room temperature afterwards, cross 325 mesh standard sieves after again the gained meal being ground and make the smart powder of carbon cladding layer expansion graphite composite negative pole material.
Embodiment 7
Lithium ion battery carbon cladding layer expansion graphite composite negative pole material has " shell-nuclear " structure, and kernel is the layer expansion graphite of Doping Phosphorus, and shell is the thermal decomposition product of phenolic resins, and the graphite layers distance is 0.3370nm.
The preparation method of above-mentioned carbon cladding layer expansion graphite composite negative pole material is as follows:
The first step: at N
2Under the atmosphere protection, crystalline flake graphite is heated to 900 ℃, constant temperature heat treatment 3h gets preliminary treatment crystalline flake graphite raw material after the cooling.
Second step: under-10 ℃ of temperature, with the pretreated crystalline flake graphite raw material of 10g, 10gNaNO
3Join the K that 150.0ml concentration is 200g/l successively with 200g formic acid
2HPO
4In the solution, leave standstill 12h after stirring, graphite: K
2HPO
4: KNO
3Mass ratio is 1: 3: 1, graphite: the formic acid mass ratio is 1: 20.Then above-mentioned viscous paste being washed to the pH value is 3, obtains the compound between graphite layers filter cake behind the vacuum filtration.
The 3rd step: the gained filter cake is added in the ethanolic solution that is dissolved with 0.625g phenolic resins, phenol resin solution concentration is 150g/ml, graphite raw material and phenolic resins mass ratio are about 16: 1, after stirring, in 100 ℃ of curing 3h, then under nitrogen and the mixed atmosphere of hydrogen, programming rate with 0.5 ℃/min is heated to 1000 ℃, constant temperature 20min is cooled to room temperature afterwards, crosses 325 mesh standard sieves after the gained meal being ground again and makes the smart powder of carbon cladding layer expansion graphite composite negative pole material.
Embodiment 8
Lithium ion battery carbon cladding layer expansion graphite composite negative pole material has " shell-nuclear " structure, and kernel is the layer expansion graphite of Doping Phosphorus, and shell is the thermal decomposition product of phenolic resins, and the graphite layers distance is 0.3377nm.
The preparation method of above-mentioned carbon cladding layer expansion graphite composite negative pole material is as follows:
The first step: at N
2Under the atmosphere protection, crystalline flake graphite is heated to 900 ℃, constant temperature heat treatment 2h gets preliminary treatment crystalline flake graphite raw material after the cooling.
Second step: under 10 ℃ of temperature, with the pretreated crystalline flake graphite raw material of 10g, 10gNaNO
3Joining 13.2ml concentration successively with 100g oxalic acid is 85% dense H
3PO
4In the solution, leave standstill 12h after stirring, graphite: H
3PO
4: NaNO
3Mass ratio is 1: 2.22: 1, graphite: the oxalic acid mass ratio is 1: 10.Then above-mentioned viscous paste being washed to the pH value is 4, obtains the compound between graphite layers filter cake behind the vacuum filtration.
The 3rd step: gained compound between graphite layers filter cake is added in the ethanolic solution that is dissolved with 0.85g phenolic resins, phenol resin solution concentration is 200g/ml, graphite raw material and phenolic resins mass ratio are about 12: 1, after stirring, solidify 3h in 120 ℃, then under nitrogen and the mixed atmosphere of hydrogen, programming rate with 0.5 ℃/min is heated to 1000 ℃, constant temperature 20min, be cooled to room temperature afterwards, cross 325 mesh standard sieves after again the gained meal being ground and make the smart powder of carbon cladding layer expansion graphite composite negative pole material.
Embodiment 9
The smart powder of the carbon cladding layer expansion graphite composite negative pole material that respectively embodiment 6-8 is made makes lithium ion battery negative, the test chemical property; As a comparison, crystalline flake graphite is ground, after 325 mesh sieves, gained-325 order graphite powder is become electrode, this is a comparative example 3.Other test condition is identical, test result such as following table:
Comparing result shows, adopt the interlamellar spacing of carbon cladding layer expansion graphite composite negative pole material of the present invention to be a bit larger tham the crystalline flake graphite material, discharge and recharge chemical properties such as reversible specific capacity under the condition, cycle life with the lithium ion battery negative of its making at 0.15C, 10C and be greatly improved.
Claims (6)
1. lithium ion battery carbon cladding layer expansion graphite composite material, it is characterized in that: composite material has the structure that shell encases kernel, and kernel is the layer expansion graphite of Doping Phosphorus, and shell is the thermal decomposition product of phenolic resins.
2. lithium ion battery carbon cladding layer expansion graphite composite material as claimed in claim 1 is characterized in that: the interlamellar spacing of kernel layer expansion graphite is 0.3360～0.3390nm.
3. a lithium ion battery as claimed in claim 1 or 2 is characterized in that with the preparation method of carbon cladding layer expansion graphite composite material: may further comprise the steps,
The first step: intercalation oxidation operation, under-10～20 ℃ of conditions, in the graphite raw material system that to impregnated in solvent be organic acid phosphoric acid or its esters with nitrate mixes, dip time is 1～24h, filtering and washing to filtrate pH value is 3～5, obtains required compound between graphite layers filter cake;
Second step: coating-delamination operation, the prepared compound between graphite layers filter cake of the first step is joined in the phenolic resins organic solution, after mixing, after curing, heat treatment, make carbon cladding layer expansion graphite composite material; Described heat-treat condition is as follows: the atmosphere that heating rate is 0.5～2 ℃/min, select for use is that mixed atmosphere, the heat treatment temperature of nitrogen or nitrogen and hydrogen is that 800～1000 ℃, constant temperature time are 10～30min.
4. the lithium ion battery as claimed in claim 3 preparation method of carbon cladding layer expansion graphite composite material; it is characterized in that: before described intercalation oxidation operation; also has the graphite raw material pretreatment process; promptly under protective atmosphere; pending graphite raw material is heated to 900～1350 ℃; constant temperature heat treatment 0.5～3h makes pretreated graphite raw material.
As claim 3 or 4 described lithium ion batteries with the preparation method of carbon cladding layer expansion graphite composite materials, it is characterized in that: in the described intercalation oxidation operation, described phosphoric acid salt is selected from a kind of in the following salt: ammonium salt, sylvite, sodium salt; Described nitrate is selected from a kind of in the following salt: ammonium salt, sylvite, sodium salt; Graphite: (phosphoric acid or its esters): the nitrate mass ratio is 1: (2.0～4.5): (0.5～1.5), graphite: the organic acid mass ratio is 1: (1～20).
6. as the preparation method of the described lithium ion battery of claim 3～5 with carbon cladding layer expansion graphite composite material, it is characterized in that: in described coating-delamination operation, be (10～16) in graphite raw material and resin quality ratio: 1 ratio is used phenolic resins organic solution; Phenolic resins organic solution solvent for use is an absolute ethyl alcohol, and phenolic resins organic solution concentration is 150～220g/ml, and the resin solidification temperature is 100～150 ℃, and be 1～4h curing time.
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