CN102530912A - Manufacturing method of boron-containing material and boron-containing material thereof - Google Patents
Manufacturing method of boron-containing material and boron-containing material thereof Download PDFInfo
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- CN102530912A CN102530912A CN2011103632917A CN201110363291A CN102530912A CN 102530912 A CN102530912 A CN 102530912A CN 2011103632917 A CN2011103632917 A CN 2011103632917A CN 201110363291 A CN201110363291 A CN 201110363291A CN 102530912 A CN102530912 A CN 102530912A
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Abstract
The present invention aims to provide a manufacturing method of a boron-containing carbon material with relatively low resistance through modification treatment on carbon material, and low-resistance boron-containing carbon material which is manufactured by the method. The manufacturing method of the boron-containing carbon material is characterized in that: through a discharge plasma sintering machine (SPS)(1), the carbon material or mixed material (7) of the carbon or carbon compound is heated through a current-flowing state, and the boron is doped in the carbon material.
Description
Technical field
The present invention relates to the method for manufacture of boracic carbon material.
Background technology
In following patent documentation 1 and patent documentation 2, relevant doped with boron in carbon nanotube is disclosed and the invention of the boracic carbon nanotube that obtains.
, in patent documentation 1, think, the resistance of boracic carbon nanotube is reduced through doped with boron under the temperature more than 2000 ℃.
But, as after shown in the experimental result stated, in heating treatment method in the past, can not fully seek the low resistanceization of boracic carbon nanotube to carbon nanotube.And, in patent documentation 1,, seek low resistanceization through more cryogenic processing though heat treated is defined as more than 2000 ℃.
In addition; In patent documentation 2 described inventions; Think to be directed on the substrate with catalyzer that chemical vapor-phase growing method capable of using makes the boracic carbon nano tube growth, but unit scale is big through mixed gas with carbon containing thing and boracic thing; And manufacturing time is long, can not make low-resistance boracic carbon nanotube in high productivity ground.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-256118 communique
Patent documentation 2: TOHKEMY 2008-222494 communique
Summary of the invention
Invent problem to be solved
The present invention accomplishes for solving above-mentioned problem in the past; Its purpose is, provides a kind of particularly the processing through the modification of carbon material can seek and the method for manufacture of the boracic carbon material of in the past comparing low resistanceization and the low-resistance boracic carbon material that utilizes this method to make.
The means that are used to deal with problems
The method of manufacture of boracic carbon material of the present invention is characterized in that,
Through the mixing material of carbon material and boron or the mixing material of carbon material and boron cpd are heated with the state that flows through electric current, boron is entrained in the said carbon material.
In the present invention, preferably heat with the mode of said mixing material not being exerted pressure from the outside.Thus, can before and after doping treatment, can keep the form of carbon material, can effectively utilize the characteristic of carbon material with the carbon material of powder state adulterated powder.
In addition, in the present invention, preferably said mixing material is heated through the mould with block (stopper is also referred to as the restraint member) function with the mode that is not under pressure.
In the present invention, preferably (Spark Plasma Sintering SPS), heats with the state that flows through electric current said mixing material, and boron is entrained in the said carbon material through the discharge plasma sinter machine.The device that the discharge plasma sinter machine normally adopts in the powder sintering; Can pressurize to switch on one side to object being treated on one side and heat; But in the present invention; As long as can keep powder and heat, even, also can access same effect therefore not to produce the device that is called energising heat-agglomerating device that plasma body is a purpose through energising.
In addition, in the present invention, adopt crystalline said carbon material in the preferred said mixing material.At this moment, through in the heating of flowing through under the state of said electric current, can the carbon atom in the crystalline structure of said crystalline carbon material be replaced into boron.
In addition, in the present invention,, preferably adopt carbon nanotube, graphite, gac, thomel or graphitized carbon as said carbon material.In addition, as said carbon nanotube, preferably adopt single-walled nanotube or many walls nanotube.
In addition, in the present invention, preferably boron shared concentration in said mixing material is adjusted in the scope of 0.1～10wt%.
In addition, in the present invention, preferably Heating temperature is adjusted in 1450 ℃～2500 ℃ the scope.If be lower than 1450 ℃ then mix insufficiently, be damaged if surpass 2500 ℃ then carbon material in addition, or surpass the fusing point of boron cpd, thereby can not obtain good characteristic sometimes.
In addition, the boracic carbon material among the present invention is characterized in that it forms through the method for manufacture described in above-mentioned.
So in the present invention; For example; Through with discharge plasma sinter machine (SPS), the mixing material of carbon material and boron or boron cpd is heated with the state that flows through electric current, boron is entrained in the said carbon material; With only carbon material (not boracic) is heated, or said mixing material is implemented patent documentation 1 described processing compare, can realize the low resistanceization of boracic carbon material.And in the present invention, also can seek the low resistanceization under the lesser temps.
The invention effect
According to the present invention, and compared in the past, but the high productivity ground and the low resistanceization of seeking the boracic carbon material at a lower temperature.
Description of drawings
Fig. 1 is the synoptic diagram of discharge plasma sinter machine (SPS).
Fig. 2 (a) is the local enlarged diagram that the part in the discharge plasma sinter machine (SPS) is amplified.
Fig. 2 (b) is the local enlarged diagram that the part in the structure discharge plasma sinter machine (SPS) different with Fig. 2 (a) is amplified.
Fig. 2 (c) is from the exert pressure local enlarged diagram of the state that forms of the state of Fig. 2 (b).
Fig. 2 (d) is a structure and (b) the local enlarged diagram that amplifies of the part in the different discharge plasma sinter machine (SPS) of Fig. 2 (a).
Fig. 3 is the powders compression density and figure than the relation of resistance value among expression comparative example 1～3 and the embodiment 1 (carbon nanotube (many walls nanotube)).
Fig. 4 (a) is the B1s spectrographic experimental result among the embodiment 1 (carbon nanotube), and Fig. 4 (b) is the B1s spectrographic experimental result in the comparative example 3.
Fig. 5 is the experimental result of the X-ray diffraction pattern of comparative example 1.
Fig. 6 is the experimental result of the Raman spectrum of comparative example 1～3 and embodiment 1 (carbon nanotube).
Fig. 7 is the synoptic diagram that constitutes the six-ring of carbon nanotube, is the explanatory view that is used for inferring the reason that the crystallinity of present embodiment descends.
Fig. 8 is the powders compression density and figure than the relation of resistance value among expression comparative example 4,5 and the embodiment 2 (graphite).
Fig. 9 is the experimental result of the Raman spectrum before and after the boron among the embodiment 2 mixes.
Figure 10 is the experimental result of the X-ray diffraction pattern of embodiment 2 (graphite).
Figure 11 is the powders compression density and figure than the relation of resistance value among expression comparative example 6 and the embodiment 3,4 (graphitized carbon).
Figure 12 is the experimental result of the Raman spectrum in embodiment 3,4 and the comparative example 6.
Figure 13 is the experimental result of the X-ray diffraction pattern of embodiment (graphitized carbon).
Figure 14 is the powders compression density and figure than the relation of resistance value in expression embodiment 5 (carbon nanotube (single-walled nanotube)) and the comparative example 7.
Figure 15 is the thermal treatment temp and figure than the relation of resistance value in expression embodiment 6 (carbon nanotube (many walls nanotube)) and the comparative example 8.
Embodiment
Fig. 1 is the synoptic diagram of discharge plasma sinter machine (SPS).
As shown in Figure 1, discharge plasma sinter machine (SPS) 1 constitutes through having upper electrode 2, lower electrode 3, sample maintenance container (mould) 4, water-cooled Vakuumkammer 5 and the DC pulse power 8 etc.
As shown in Figure 1, keep the front end of container 4 sides at the sample of upper electrode 2 and lower electrode 3, be provided with the lid material 6,6 that for example constitutes by carbon.Have, sample keeps container 4 for example also to be formed by carbon again.
In sample kept container 4, being filled with carbon material was that carbon nanotube (CNT) is the mixing material 7 of boron or boron cpd with dopant material.Preferably adopt B as boron cpd
4The C powder.Perhaps also can adopt B as boron cpd
2O
3About the blending means of carbon nanotube and boron or boron cpd, can select existing method.For example, do not make boron cpd form powder, and shown in Fig. 2 (a), can and establish multi-disc borated graphite plate 10, filling carbon nano-pipe 11 betwixt.But, make boron cpd form powder and compare with adopting borated graphite plate 10, fasten in the pass of diffusion length, can improve the electroconductibility of the boracic carbon material of manufacturing.
Here, boron shared concentration in mixing material 7 is preferred about 0.1～10wt%.Thus, but the low resistanceization that the boracic carbon nanotube is sought on high productivity ground.
In this embodiment; Its purpose is not the sintering of mixing material, but the modification of carbon nanotube processing, therefore; For example; Following formation can be proposed, that is: do not use be connected on the front end that covers material 6,6 or electrode 2,3 and be used for from up and down to being filled in top drift (not shown) and the bottom drift (not shown) that sample keeps the samples in the container 4 to pressurize the strong stress when not applying like sintering to mixing material 7.Having, also can keep the mixing material in the container 4 to be filled in and to cover between the material 6 with complete mode very close to each other on the sample of packing into shown in Figure 1, perhaps, also can be the state that between mixing material 7 and lid material 6, produces some gaps (space).
But, exert pressure a little in the time of in mixing material 7 being filled into sample maintenance container 4.And after filling, preferably do not heat from the outside to mixing material 7 with exerting pressure.The mixing material 7 of this embodiment can use as powder without sintering.Therefore, through not heating, follow-uply need not pulverize from the outside to mixing material 7 with exerting pressure.If the enforcement pulverizing process, then crystalline structure is destroyed, and is difficult to control size distribution.In addition, under the situation of the carbon material that adopts carbon nanotube or the isometric size of carbon nanofiber,, then be divided into shortlyer, can not keep the form at initial stage if the carbon material that sintering is for the time being formed is pulverized, thus the abundant characteristic that has of Material Used.In this embodiment, do not need pulverizing process, thereby can suitably be had the powder of low-resistance value simply.
In this embodiment, the mode that preferably is not under pressure with mixing material 7 heats through the mould that possesses block mechanism.
Except that Fig. 1, Fig. 2 (a), shown in Fig. 2 (b), in the time of in mixing material 7 being filled into sample maintenance container 4; Through drift 15,16 pressurize (pressing shown in the arrow); This moment, lid material 6,6 and sample kept the butt up and down of container 4 shown in Fig. 2 (c), and; Can flow through electric current with the pressure status that does not receive from the outside to mixing material 7, carry out heat treated simultaneously.Fig. 2 (b) (c) in, sample keeps the upper surface 4a of container 4 and lower surface 4b to play a role as block with respect to drift 15,16 (lid material 6,6).
Perhaps, shown in Fig. 2 (d), the drift 17,18 that also can adopt the drift 15,16 of Fig. 2 (b) shown in (c) and lid material 6 to become one.If to drift 17,18 pressurizations, then the extension 17a of drift 17,18,18a and sample keep the upper surface 4a and the lower surface 4b butt of container 4, and mixing material 7 is not under pressure.
With forming vacuum (for example 0.04torr) in the water-cooled Vakuumkammer shown in Figure 15,, drop into pulse high current (for example 5KA) with low voltage through the DC pulse power 8.Thus, via lid material 6 from electrode 2,3 to mixing material 7 and sample keep container 4 to flow through pulse high current.Thus, the Heating temperature of mixing material 7 is risen rapidly, a gas rises to about 2000 ℃.Then this state is kept about dozens of minutes.Thus, boron is entrained in the carbon nanotube.Have again, when the boracic carbon nanotube that in sample keeps container 4, takes out this embodiment, as required the boracic carbon nanotube is separated with untapped boron cpd or impurity.
Can use boracic carbon nanotube in this embodiment as electronic unit or structured material.For example, can be used as electro-conductive material, resistive material, double layer capacitor with electrode, Li electrode for secondary battery or electrode for fuel cell through with pulverous boracic carbon nanotube and mixed with resin.
As stated, in this embodiment, heat with the mixing material 7 of discharge plasma sinter machine (SPS) to carbon nanotube and boron cpd.In this embodiment, flow through mixing material 7 through making pulse high current, Heating temperature is risen to about 2000 ℃, boron is entrained in the carbon nanotube.Have again, when pulse high current is flow through, also can consider to generate plasma body.Boron is entrained in the processing in the carbon nanotube in this embodiment; Different with chemical vapor-phase growing method shown in sintering or the patent documentation 2 etc.; Refer under stressed state very strong not receiving when in the sample of discharge plasma sinter machine (SPS) keeps container 4, carrying out sintering the surface modification treatment that mixing material 7 is heated with discharge plasma sinter machine (SPS).That is, in this embodiment, can doped with boron even mixing material 7 is not directly pressurizeed yet, compare with example in the past and can reach low-resistance value.In this embodiment, preferably mixing material 7 is filled in the sample maintenance container 4 of discharge plasma sinter machine (SPS), heat with the state (not having pressurization) of mixing material 7 not being exerted pressure from the outside.But, preferably when filling mixing material 7, exert pressure.In this embodiment, when heating, directly limit, so that mixing material 7 is not under pressure.Here so-called do not have a pressurization, means not to be the formation of intentionally mixing material 7 being exerted pressure, and the situation that is under pressure a little finally is not for there being pressurization yet.For example, when lid material shown in Figure 16,6 was applied the pressure of regulation, sample kept the mixing material 7 in the container 4 to be under pressure; But this moment; Some lid materials 6,6 enter into the inside that sample keeps container 4, or because of the many upward pressures as a result of amount of mixing material 7 act on mixing material 7, the sample that perhaps causes because of heating keep the expansion in the container 4 etc. as a result upward pressure play a role; Above-mentioned formation does not meet the state of exerting pressure from the outside wittingly, thereby is defined as the nothing pressurization.
According to this embodiment, through above-mentioned method of manufacture, and carbon nanotube (not boracic) is heated with process furnace, perhaps mixing material is implemented patent documentation 1 described processing and compare, can seek the low resistanceization of boracic carbon nanotube.
In addition, according to this embodiment, can seek the low resistanceization under the lesser temps about 1450 ℃～2500 ℃.In this embodiment, more preferably Heating temperature is set in below 2000 ℃.
In addition, can the diameter of the boracic carbon nanotube that forms through above-mentioned method of manufacture be adjusted to more than the 10nm.
Have again, in this embodiment, except that carbon nanotube, also can adopt carbon black, graphite, Graphene, gac, thomel, graphitized carbon etc. as carbon material.As carbon nanotube, can adopt single-walled nanotube (SWCNT) or many walls nanotube (MWCNT).In this embodiment, can adopt multiple carbon material like this, but through adopting crystalline carbon material, can low resistanceization in the method for manufacture of this embodiment and the low resistance of utilizing the crystallization progress divided out and realized.Why supposition can separate and realize, is because can promote the displacement of the C element in crystalline structure of crystallinity carbon to the B element, thereby can seeks low resistanceization effectively.Crystalline carbon material in this embodiment refers to the state in the mixing material 7 before the heating.Promptly do not comprise initial (before the heating) for example for non-crystalline state but through heating the carbon of crystallization.
In this embodiment,, preferably select in carbon nanotube (single-walled nanotube or many walls nanotube), graphite, gac, thomel or the graphitized carbon any as crystalline carbon material.Adopt which kind of material as carbon material, can carry out multiple choices than resistance (electroconductibility) etc. according to use is desired.But,, can reduce ratio resistance value (raising electroconductibility) effectively with respect to powders compression density through adopting carbon nanotube.
The formation of this embodiment is characterised in that: through mixing material 7 is heated with the state that flows through electric current; Boron is entrained in the carbon material; The method that realizes this formation is unqualified; But shown in the experimental result described as follows,, preferably adopt discharge plasma sinter machine (SPS) as effective means.
Embodiment
(adopting the experiment of carbon nanotube (many walls nanotube))
Adopt carbon nanotube (clear many walls nanotube (model VGCF) made from the electrician), the sample below preparing.
(comparative example 1)
The carbon nanotube article (raw state when buying) that are untreated
(comparative example 2)
In argon gas, the item for disposal of under 2000 ℃, 30 minutes condition, carbon nanotube being handled to obtain
(comparative example 3)
The B that in carbon nanotube, mixes 3wt%
4C (in the mixing material with respect to the B element of carbon nanotube) and obtain mixing material, in argon gas, the item for disposal of under 2000 ℃, 30 minutes condition, mixing material being handled to obtain
(embodiment 1)
The B that in carbon nanotube, mixes 2.5wt%
4C (in the mixing material with respect to the B element of carbon nanotube) and obtain mixing material, in a vacuum, the item for disposal of under 2000 ℃, 30 minutes condition, mixing material being handled to obtain with discharge plasma sinter machine (SPS)
The ratio of pulse length to the total cycle length of pulsed current is defined as 6: 1, heat-up rate is defined as 30 ℃/minute, will be defined as 30MPa the stress of the lid material 6 of Fig. 1.Have, this moment is owing to not directly to the mixing material pressurization, therefore be to be called the state that does not have pressurization again.But, mixing material applied mixing material be filled into sample keep required pressure in the container.
Fig. 3 is the powders compression density and figure than the relation of resistance value among expression comparative example 1～3 and the embodiment 1.
As shown in Figure 3, in comparative example 1～3 and embodiment 1 whole, find that powders compression density is big more, descend more than resistance value.
In addition, as shown in Figure 3, learn: when seeing with identical powders compression density, embodiment 1 compares with comparative example 1～3, necessarily can reduce and compare resistance value.In addition, in embodiment 1, can even be lower than 2000 ℃ Heating temperature in addition, compare, also can realize low resistance in the low resistance below realizing about 0.2 (Ω cm) under the Heating temperature about 2000 ℃ with comparative example.So according to present embodiment; Compare with comparative example; Can make boracic carbon nanotube low resistanceization, and can set the required Heating temperature of low resistanceization at a lower temperature, can be suppressed at and produce such unfavorable condition of defective or the such unfavorable condition of carbon nanotube decomposition in the carbon nanotube.
Then, through XPS (x-ray photoelectron power spectrum) formation element and the B1s spectrum of above-mentioned comparative example 1～3 and embodiment 1 are measured.Constitute the analytical results of element shown in the following table 1.
Table 1
As shown in table 1, mixing carbon nanotube and B
4In the comparative example 3 and embodiment 1 of C, boron (B) is confirmed to be the formation element.
Fig. 4 (a) is the B1s spectrographic experimental result among the embodiment 1, and Fig. 4 (b) is the B1s spectrographic experimental result in the comparative example 3.
Shown in Fig. 4 (a), Fig. 4 (b), all see the B-C bonding in embodiment 1 and the comparative example 3, but in the comparative example 3 of Fig. 4 (b), see bonding a plurality of and O or N, think that B-C is bonded among the embodiment 1 more than comparative example 3.
Then, measured the crystalline state of comparative example 1～3 and embodiment 1 through X-ray diffraction method.Fig. 5 illustrates the X-ray diffraction pattern of comparative example 1.Absolute value), among comparative example 2,3 and the embodiment 1 and d value difference (interplanar crystal spacing is poor) comparative example 1 the diffraction angle (2 θ) of C shown in the table 2 (002) crystal face, C (004) crystal face, C (110) crystal face, the d value in the comparative example 1 (interplanar crystal spacing:.
Table 2
As shown in table 2, learn: comparative example 1～3 is roughly the same interplanar crystal spacing.Relative therewith, in embodiment 1, the interplanar crystal spacing of C (002) crystal face, C (004) crystal face and comparative example 1～3 somewhat narrower some (the interplanar crystal spacing difference is a negative value).
In addition, as shown in table 2, learn: in embodiment 1, that the interplanar crystal spacing of C (110) crystal face is compared with comparative example 1～3 is wideer slightly (interplanar crystal spacing difference on the occasion of).So embodiment 1 compares with comparative example 1～3 and in crystalline structure, finds some distortion.
Then utilize Raman spectroscopy that comparative example 1～3 and embodiment 1 are measured.The laser Raman spectrometer that Raman spectroscopy adopts Horiba Jobin Yvon to make.
Fig. 6 illustrates the experimental result of the Raman spectrum of comparative example 1～3 and embodiment 1.G bands of a spectrum shown in Figure 6 demonstrate crystallinity, and the D bands of a spectrum demonstrate amorphism.Think to be lower than under the state (crystallinity descend state) of D bands of a spectrum, be the incomplete state of formation of the six-ring that constitutes carbon nanotube at the G bands of a spectrum.Value at each G/D of comparative example 1～3 shown in the following table 3 and embodiment 1.
Table 3
| 1 | 2 | 3 | AVE | |
| Comparative example 1 | 4.5 | 8 | 6.25 | |
| Comparative example 2 | 5.2 | 7 | 6.10 | |
| Comparative example 3 | 1.66 | 2.11 | 1.70 | 1.82 |
| |
1.15 | 1.05 | 1.14 | 1.11 |
Shown in the table 3 each sample measured G/D the result and the MV of secondary or three times.
As shown in table 3, embodiment 1 compares G/D with comparative example 1～3 and reduces.Find that like this embodiment 1 compares crystallinity and reduces with comparative example 1～3, but this is for example as shown in Figure 7, thinks that it is not one of reason that a part of carbon (C) with six-ring is replaced as boron (B).Infer that this is also because the interplanar crystal spacing of C (110) crystal face shown in the table 2 has enlarged some slightly in embodiment 1.Promptly; Think that the expansion of interplanar crystal spacing of C (110) crystal face is not because the bond distance of six-ring has enlarged some; If the experimental result of Raman spectrum is also coincide; Then as shown in Figure 7, supposition is to be replaced as boron (B) through a part of carbon (C) with six-ring to make the bond distance produce difference, and crystalline structure produces distortion (crystallinity decline).
Above-mentioned carbon (C) and boron (B) though displacement in the processing of comparative example 3, also produce, compare with the present embodiment that utilizes discharge plasma sinter machine (SPS) to handle think small.
Think that so through the displacement of carbon (C) with boron (B), (hole hole) increases, thereby promoted low resistanceization (electroconductibility) to make carrier.
(adopting the experiment of graphite)
As graphite, adopting particle diameter is that (SEC Carbon makes, SNO3) for the flaky graphite of 3 μ m.In addition, as dopant material, the particle diameter that has added 3wt% in the B element with respect to graphite is the B of 8 μ m
4C.
Comparative example 4 and above-mentioned comparative example 1 are same, do not carry out any processing.Comparative example 5 adopts and comparative example 3 same creating conditions.Embodiment 2 adopts and embodiment 1 identical creating conditions.
Fig. 8 is the powders compression density and figure than the relation of resistance value among expression comparative example 4,5 and the embodiment 2 (graphite).
As shown in Figure 8, embodiment 2 compares with comparative example 4,5, the ratio resistance value in the time of can reducing under the same powder pressed density, to compare.(in powders compression density is 0.5g/cm particularly can the ratio resistance value of embodiment 2 to be reduced about 1/6 with respect to the ratio resistance value of comparative example 4 (article are untreated)
3Part measure).In other words, the electroconductibility of embodiment 2 is compared with comparative example 4 and can be brought up to about 6 times.Even in addition in comparative example 5, can reduce than resistance although compare with comparative example 4, can access frequently the lower ratio resistance of example 5 in the present embodiment.
Fig. 9 is the experimental result of the Raman spectrum before and after the boron among the embodiment 2 mixes.The laser Raman spectrometer that Raman spectroscopy adopts Horiba Jobin Yvon to make.G/D lists in the following table 4.Have again,, respectively detect secondary before the doping treatment and after the doping treatment, obtain MV for G/D.
Table 4
If the sexangle stratum reticulare of graphite correctly forms, G bands of a spectrum grow then, when when the part shortcoming C element of sexangle stratum reticulare or C element take place to replace with the B element, the D bands of a spectrum scattering peak occurs in identical position.
Shown in Fig. 9 and table 4, after doping treatment, G/D is approximately 1/4, thinks thus, has produced C element and the displacement of B element in the sexangle stratum reticulare of graphite.
Then, investigate the variation of interplanar crystal spacing through XRD determining.Figure 10 is the experimental result of the X-ray diffraction pattern of embodiment 2 (graphite).In addition, the d value (interplanar crystal spacing: absolute value) before and after the doping treatment of C shown in the following table 5 (002) crystal face, C (103) crystal face, C (105) crystal face.
Table 5
Figure 10 is illustrated in the Miller indices at the peak that mainly occurs in the X-ray diffraction pattern of graphite.As shown in table 5, learn: the interplanar crystal spacing of C (002) crystal face reduces after doping treatment, and promptly the C direction of principal axis narrows down, and on the other hand, the interplanar crystal spacing of C (103) crystal face and C (105) crystal face increases after doping treatment, promptly expands along a direction of principal axis.Infer that this is because through doping treatment C element and B element substitution.
Then, through XPS (x-ray photoelectron power spectrum) assay determination formation element and the B1s spectrum among the embodiment 2.Constitute the analytical results of element shown in the table 6.
Table 6
In addition, as the B of dopant material
4The spectrographic B-B of C, B-C are approximately 1 ratio, through with its with doping treatment after B1s spectrum compare, learn: also have 0.4% even B concentration is minimum, it is about 27% that the B-C bonding exists, and the B-O bonding exists about 13%.
As previously discussed, through doped with boron in graphite, with respect to the graphite that does not carry out doping treatment, electroconductibility is brought up to about 6 times.Doping in graphite increases the possibility of C element and B element substitution in the sexangle stratum reticulare, thinks that thus the hole as carrier increases, and electroconductibility increases.
(adopting the experiment of graphitized carbon)
As graphitized carbon, the #3845 that adopts East Sea carbon to make.As dopant material, the particle diameter that adds 2.5wt% in the B element with respect to graphitized carbon is the B of 50 μ m or 0.8 μ m in addition
4C.
Comparative example 6 and above-mentioned comparative example 1 are same, also do not carry out any processing.Embodiment 3,4 adopts and embodiment 1 identical creating conditions.In addition, in embodiment 3, adopting particle diameter is the B of 50 μ m
4C.Adopting particle diameter among this external embodiment 4 is the B of 0.8 μ m
4C.
Figure 11 is the powders compression density and figure than the relation of resistance value among expression comparative example 6 and the embodiment 3,4 (graphitized carbon).
Shown in figure 11, embodiment 3,4 compares with comparative example 6, the ratio resistance value in the time of can reducing under the same powder pressed density, to compare.Particularly, (in powders compression density is 0.5g/cm can the ratio resistance value of embodiment 3,4 to be reduced about 1/6 with respect to the ratio resistance value of comparative example 6 (article are untreated)
3Part measure).In other words, the electroconductibility of embodiment 3,4 is compared with comparative example 6 and is brought up to about 6 times.
In addition, Figure 11 is different with Fig. 8, without comparison the experimental result of item for disposal (being called example in the past here) shown in the example 5, that get about mixing material is handled under 2000 ℃, 30 minutes condition in argon gas; If but with Fig. 8 contrast, 3,4 of embodiment among Figure 11 are same with the embodiment 2 among Fig. 8, can be with reducing about 1/6 with respect to comparative example 6 than resistance value; So; Think with Fig. 8 likewise, compare with example in the past and can reduce can obtain high conductivity than resistance.
At B
4Among the embodiment 3 that the particle diameter of C has difference and the embodiment 4, not finding has significant difference than resistance, but what find to have mixed small particle size is that particle diameter is the B of 0.8 μ m
4The effect that the electroconductibility of the embodiment 4 of C further improves.
Figure 12 is the experimental result of the Raman spectrum that (is comparative example 6 before mixing) before and after the doping of embodiment 3,4.The laser Raman spectrometer that Raman spectroscopy adopts Horiba Jobin Yvon to make.In addition, G/D lists in the following table 7.Have again, respectively measure respectively three times, obtain MV for G/D.
Table 7
If the sexangle stratum reticulare of graphite correctly forms, G bands of a spectrum grow then, when when the part shortcoming C element of sexangle stratum reticulare or C element and B element have carried out displacement, the D bands of a spectrum scattering peak occurs in identical position.
Shown in Figure 12 and table 7, the G/D of embodiment after the doping treatment 3 and embodiment 4 is about 0.6, compares with (G/D=1.32) before the doping treatment (comparative example 6) to reduce by half.Think thus, produced C element and the displacement of B element in the sexangle stratum reticulare of graphitized carbon.
Then, investigate the variation of interplanar crystal spacing through XRD determining.Figure 13 is the experimental result of the X-ray diffraction pattern of embodiment 3,4 (graphitized carbons).In addition, the d value (interplanar crystal spacing: absolute value) of C (002) crystal face in embodiment shown in the following table 83,4 and the comparative example 6, C (100) crystal face, C (004) crystal face, C (110) crystal face.
Table 8
Figure 13 is illustrated in the Miller indices at the peak that mainly occurs in the X-ray diffraction pattern of graphitized carbon.As shown in table 8; Learn: the interplanar crystal spacing of C (002) crystal face, C (004) crystal face reduces than comparative example 6 after doping treatment; Be that the C direction of principal axis narrows down; On the other hand, the interplanar crystal spacing of C (100) crystal face and C (110) crystal face is different because of the kind of the particle diameter of dopant material and crystal face with respect to the increase and decrease of comparative example 6 tendency.Though be that the C direction of principal axis narrows down because of doping treatment, change according to dopant material to a direction of principal axis, thinking does not have unified tendency.
Then, through XPS (x-ray photoelectron power spectrum) assay determination formation element and the B1s spectrum in embodiment 3,4 and the comparative example 6 (article are untreated).Constitute the analytical results of element shown in the table 9.
Table 9
Have again, to the B1s spectrum after the doping treatment and as the B of dopant material
4The spectrum of C tries to compare, but in both, does not find big difference.
As previously discussed, through B that graphitized carbon is mixed
4The processing of C, with respect to the graphitized carbon that does not carry out doping treatment, electroconductibility is brought up to about 6 times.Have again, approximately reduce by half than after doping, obtained being regarded as replacing result thus, but do not found to hint the significant displacement of C-B metathetical from the experimental result of XRD carrying out as the G/D of the Raman of the C-B metathetical benchmark in the sexangle stratum reticulare in the graphite portion.Infer that thus the C-B metathetical ratio of graphitized carbon is lower than the ratio of carbon nanotube or graphite.
(adopting the experiment of carbon nanotube (single-walled nanotube))
Adopt single-walled nanotube (well-known city carbon is made, model FH-P), the sample below preparing.
(comparative example 7)
The single-walled nanotube article (raw state when buying) that are untreated
(embodiment 5)
The B that in single-walled nanotube, mixes 3wt%
2O
3(in the mixing material) and obtain mixing material in B element with respect to single-walled nanotube, with discharge plasma sinter machine (SPS), the item for disposal of under 1450 ℃, 30 minutes condition, mixing material being handled to obtain in a vacuum
The ratio of pulse length to the total cycle length of pulsed current is defined as 6: 1, heat-up rate is defined as 30 ℃/minute, will be defined as 30MPa the stress of the lid material 6 of Fig. 1.Have, this moment is owing to not directly to the mixing material pressurization, therefore be to be called the state that does not have pressurization again.But, mixing material applied mixing material be filled into sample keep required pressure in the container.
Figure 14 is the powders compression density and figure than the relation of resistance value among expression comparative example 7 and the embodiment 5.
Shown in figure 14, in comparative example 7 and embodiment 5 whole, find that powders compression density is big more, descend more than resistance value.
In addition, shown in figure 14, learn: embodiment 5 compares with comparative example 7, when seeing with identical powders compression density, necessarily can reduce and compare resistance value.In addition, in embodiment 5, can be in the low resistance below realizing about 0.5 (Ω cm) under the Heating temperature about 1450 ℃.
Then, likewise adopt single-walled nanotube and B with embodiment 5
2O
3, B element cooperation ratio is changed, having measured powders compression density is 0.4g/cm
3The time ratio resistance value and G/D ratio.Its experimental result is shown in following table 10.
Table 10
As shown in table 10, even the concentration of B element is increased to 10wt%, compare also can reduce with comparative example 7 and compare resistance value.In addition, embodiment compares G/D with comparative example 7 and reduces.Infer thus: in an embodiment, be replaced as boron (B) through the carbon (C) with the part of six-ring and make the bond distance produce difference, crystalline structure produces distortion (crystallinity decline).So think,, carrier (hole) is increased, thereby promoted low resistanceization (electroconductibility) through the displacement of carbon (C) with boron (B).
(experiment of relevant thermal treatment temp)
Adopt carbon nanotube (clear many walls nanotube (model VGCF) made from the electrician), the sample below preparing.
(comparative example 8)
The B that in carbon nanotube, mixes 3wt%
4C (in the mixing material) and obtain mixing material, the item for disposal of under 1400 ℃～2000 ℃, 30 minutes condition, mixing material being handled to obtain in a vacuum in B element with respect to carbon nanotube
(embodiment 6)
The B that in carbon nanotube, mixes 3wt%
4C (in the mixing material) and obtain mixing material, the item for disposal of under 1400 ℃～2000 ℃, 30 minutes condition, mixing material being handled to obtain in a vacuum with discharge plasma sinter machine (SPS) in B element with respect to carbon nanotube
The ratio of pulse length to the total cycle length of pulsed current is defined as 6: 1, heat-up rate is defined as 30 ℃/minute, will be defined as 30MPa the stress of the lid material 6 of Fig. 1.Have, this moment is owing to not directly to the mixing material pressurization, therefore be to be called the state that does not have pressurization again.But, mixing material applied mixing material be filled into sample keep required pressure in the container.
Figure 15 is the thermal treatment temp and figure than the relation of resistance value among expression comparative example 8 and the embodiment 6.Have, the powders compression density unification of each sample is defined as 0.4g/cm again
3
Shown in figure 15, learn: if the heat treated temperature rises then descends than resistance value.If but the heat treated temperature reaches more than 1800 ℃, then the reduction effect than resistance value reduces.
Shown in figure 15, learn: for example,, then can thermal treatment temp be reduced about 100 ℃～200 ℃ if obtain the ratio resistance value roughly the same with comparative example 6 through embodiment.Perhaps, in embodiment 6 and comparative example 8,, can expect that also embodiment makes the value that is reduced to regulation than resistance value in the time shorter than comparative example even be defined as identical heat treated temperature.
So embodiment 6 compares with comparative example 8, can realize the short period of timeization of low temperatureization and heat treatment step.Can seek thus to save the energy and boost productivity.
Following table 11 is experimental results of measuring the G/D ratio of each sample shown in Figure 15.Also show the ratio resistance value and the G/D ratio of the article that are untreated of carbon nanotube in the table 11 in the lump.
Table 11
As shown in table 11, embodiment compares G/D with comparative example and the article of being untreated and reduces.Infer that thus in an embodiment, be replaced as boron (B) through the carbon (C) with the part of six-ring and make the bond distance produce difference, crystalline structure produces distortion (crystallinity decline).So think,, carrier (hole) is increased, thereby promoted low resistanceization (electroconductibility) through the displacement of carbon (C) with boron (B).
(experiment of relevant ratio of pulse length to the total cycle length)
Ratio of pulse length to the total cycle length at pulsed current is 99: 1, and Heating temperature is 1600 ℃, handles under the identical condition of other condition and embodiment 6, prepares sample (embodiment 7).Prepared the comparative example 8 of the article that are untreated in addition.Embodiment 7 is measured with the powder resistance value of each sample of embodiment 6 that under identical temperature, has carried out heating and comparative example 8.Its experimental result is shown in following table 12.
Table 12
| Ratio of pulse length to the total cycle length | Powder resistance value (Ω cm) | |
| |
6∶1 | 0.051 |
| |
99∶1 | 0.062 |
| Comparative example 8 | - | 0.102 |
Have, the powder resistance value representation powders compression density shown in the table 12 is 0.4g/cm again
3The time the ratio resistance value.As shown in table 12, even in embodiment 7, compare the powder resistance value with comparative example 8 and also reduce, demonstrate effect of the present invention.In addition, powder resistance is inequality in having only ratio of pulse length to the total cycle length various embodiment 6 and embodiment 7, we can say and has confirmed through pulsed current doping treatment have been applied influence.
Nomenclature
1 discharge plasma sinter machine (SPS)
2,3 electrodes
4 samples keep container (mould)
5 water-cooled Vakuumkammers
6 lid materials
7 mixing materials
The 8DC pulse power
10 borated graphite plates
11 carbon nanotubes
15～18 drifts
Claims (11)
1. the method for manufacture of a boracic carbon material is characterized in that, through the mixing material of carbon material and boron or the mixing material of carbon material and boron cpd are heated with the state that flows through electric current, boron is entrained in the said carbon material.
2. the method for manufacture of boracic carbon material according to claim 1 wherein, heats with the mode of from the outside said mixing material not being exerted pressure.
3. the method for manufacture of boracic carbon material according to claim 2 wherein, heats through the mould with block function with the mode that is not under pressure said mixing material.
4. the method for manufacture of boracic carbon material according to claim 1 wherein, through the discharge plasma sinter machine, heats with the state that flows through electric current said mixing material, and boron is entrained in the said carbon material.
5. the method for manufacture of boracic carbon material according to claim 1 wherein, adopts crystalline said carbon material in the said mixing material.
6. the method for manufacture of boracic carbon material according to claim 5, wherein, the heating through under the said state that flows through electric current is replaced into boron with the carbon atom in the crystalline structure of said crystalline carbon material.
7. the method for manufacture of boracic carbon material according to claim 1 wherein, as said carbon material, adopts carbon nanotube, graphite, gac, thomel or graphitized carbon.
8. the method for manufacture of boracic carbon material according to claim 7 wherein, as said carbon nanotube, adopts single-walled nanotube or many walls nanotube.
9. the method for manufacture of boracic carbon material according to claim 1 wherein, is adjusted to boron shared concentration in said mixing material in the scope of 0.1～10wt%.
10. the method for manufacture of boracic carbon material according to claim 1 wherein, is adjusted to Heating temperature in 1450 ℃～2500 ℃ the scope.
11. a boracic carbon material is characterized in that, it forms through each described method of manufacture in the claim 1～10.
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| JP247087/2011 | 2011-11-11 |
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| CN109311674A (en) * | 2016-06-15 | 2019-02-05 | 国立大学法人东北大学 | Carbon material and its manufacturing method |
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| CN114735690A (en) * | 2022-04-19 | 2022-07-12 | 湖南铂威新能源科技有限公司 | Preparation method of artificial graphite composite negative electrode material for lithium ion battery |
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| CN105399077A (en) * | 2015-12-09 | 2016-03-16 | 中南大学 | Preparation method of atom doped carbon material in physical field |
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| CN114735690A (en) * | 2022-04-19 | 2022-07-12 | 湖南铂威新能源科技有限公司 | Preparation method of artificial graphite composite negative electrode material for lithium ion battery |
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