JPH10308221A - Manufacture of carbon material for negative electrode of now-aqueous solvent secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a carbon material for negative electrode of non-aqueous solvent secondary battery, which have a high capacity and high performance, at a low cost by reforming a precursor pitch, which is obtained by polymerizing condensation polycyclic compound including a methyl group in the existence of hydrogen fluoride and boron trifluoride, and performing the infusible processing to the obtained reformed pitch, and thereafter, burning it. SOLUTION: A condensation polycyclic compound, which includes one or more methyl group such as a di-methylnaphthalene, is polymerized at 0-300 deg.C in the existence of hydrogen fluoride and boron trifluoride so as to obtain a precursor pitch or tar, which has a softening point at 0-180 deg.C, a ratio of carbon to hydrogen at 0.70-1.10, pyridine insoluble matter at 1.0% or less, and a ratio of aliphatic hydrogen in the whole of hydrogen at 30-80%. This precursor pitch or tar is reformed by flowing air at 200 deg.C or more or the like so as to obtain the 100% optically isotropic reformed pitch or tar, which has a softening point at 150-300 deg.C, a ratio of carbon to hydrogen at 0.50-0.80, C-H expansion absorption intensity ratio of aliphatic group and aromatic group of FT-IR measurement at 0.5 or more. Infusible processing is performed to the reformed pitch or tar at 100-400 deg.C in the existence of the oxidant gas, and thereafter, the reformed pitch or tar is burned at 800-1800 deg.C in the existence of the non- oxidant gas or in the vacuum.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a carbon material for a negative electrode of a non-aqueous solvent secondary battery having a large capacity and a small irreversible capacity.

[0002]

2. Description of the Related Art A non-aqueous solvent secondary battery using a carbon material for a negative electrode has already been put into practical use as a lithium ion secondary battery because of its advantages such as high energy density, light weight, small size and long-term storage. However, it is necessary to increase the capacity of the carbon material for the negative electrode in order to cope with the reduction in size and weight of electronic devices. Therefore, for example, as described in JP-A-6-187988, by reacting pitch or tar with a nitro compound, a high-capacity carbon material having a discharge capacity per weight exceeding 500 mAh / g has been found. Issued and considered. However, there is a great demand for the development of a lithium ion secondary battery that can be operated for a longer time, and the materials used up to now have been insufficient to meet the demand for capacity. So far, it has been found that coke fired at a low temperature or polyacene fired with phenolic resin has a high capacity. However, while the capacity is improved, the irreversible capacity (the first cycle) which is disadvantageous when a secondary battery is used is considered. The difference between the charge capacity and the discharge capacity at
It was not enough to meet the demand. Furthermore, at the time of discharge,
Since the potential of the negative electrode material with respect to lithium metal is high, a major drawback is that the average voltage when a secondary battery is designed in combination with the positive electrode material is low.

[0003]

As described above, the conventional non-aqueous solvent-based lithium secondary battery using a carbon material as a negative electrode material is not sufficient for realizing a large capacity which is a characteristic of the non-aqueous solvent-based lithium secondary battery. Was. SUMMARY OF THE INVENTION The present invention overcomes the above-mentioned conventional problems and provides a high-capacity, high-performance non-aqueous solvent secondary battery with good charge / discharge cycle characteristics and excellent stability and safety. ) Having a high capacity of 500 mAh / g or more per weight, 2) reducing the irreversible capacity of the carbon material for the negative electrode in the first cycle, and 3) reducing the potential of the negative electrode material to lithium metal at the time of discharge to 0.2 V or less. An object is to provide a carbon material for a negative electrode having a large capacity in a certain region.

[0004]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on a high-capacity carbon material for a negative electrode using pitch or tar as a raw material. Alternatively, a specific precursor pitch or tar obtained by synthesis from a substance containing the same is modified into a specific modified pitch, and after infusibilizing the modified pitch, the carbon material obtained by firing is a non-aqueous solvent. The inventors have found that they have excellent properties as a negative electrode of a secondary battery, and have completed the present invention.

The carbon material for a negative electrode of a non-aqueous solvent secondary battery of the present invention is obtained by polymerizing a specific condensed polycyclic compound or a substance containing the same in the presence of hydrogen fluoride / boron trifluoride. A non-aqueous solvent characterized by being prepared by modifying a precursor pitch or tar of a non-aqueous solvent, preparing a specific modified pitch or tar, infusibilizing the same with an oxidizing gas, and then firing. It is a carbon material for a secondary battery negative electrode.

Examples of the condensed polycyclic compound containing one or more methyl groups or a substance containing the same as a raw material of a precursor pitch or tar to be synthesized include condensed polycyclic hydrocarbons such as naphthalene, anthracene, pyrene and coronene. Derivatives containing one or more methyl groups, derivatives containing one or more methyl groups of condensed heterocyclic compounds such as benzofuran, quinoline, tianaphthalene, silanaphthalene, and mixtures of condensed polycyclic compounds with them, Coal tar fraction, petroleum fraction, residual oil of petroleum processing step, etc. are used. In particular, naphthalene derivatives such as methylnaphthalene and dimethylnaphthalene, and a methylnaphthalene fraction of coal tar as a mixture thereof, ethylene bottom oil, and the like are preferable for the performance as a carbon material for a negative electrode described later and the infusibilization step.

The method of synthesizing the precursor pitch or tar from the condensed polycyclic compound in the presence of a hydrogen fluoride / boron trifluoride catalyst is not particularly limited. 0.1 to 10 mol of hydrogen fluoride, 0.01 to 1.0 mol of boron trifluoride, the reaction temperature is in the range of 0 to 300 ° C, preferably 40 to 100 mol per mol of the cyclic compound.
The reaction is performed at 200 ° C, more preferably at 60 to 170 ° C.

As a property of the precursor pitch or tar obtained from the condensed polycyclic compound, the softening point is 0-18.
The temperature is preferably 0 ° C, more preferably 20 to 150 ° C. Further, the atomic ratio of hydrogen to carbon is 0.7 to 1.1.
0, the pyridine-insoluble content is preferably 1.0% or less, and the proportion of aliphatic hydrogen in the total hydrogen contained in the pitch is preferably 30 to 80%. After polishing the precursor pitch or tar by a conventional method, the optical structure when observed under a polarizing microscope is 1
It is 00% isotropic.

Next, the precursor pitch or tar is treated with modified pitch or tar having a softening point of 150 ° C. or higher while maintaining optical isotropy. The reforming can be performed by a known method such as distillation, air blowing, addition of nitric acid, and addition of sulfur. Among them, a method in which an oxidizing gas, generally air is passed through pitch or tar in a fluidized state under heating is simple, inexpensive and effective. Although the temperature at this time cannot be specified unconditionally by the softening point of the precursor pitch or tar, it is carried out at 200 ° C. or more, preferably 300 to 350 ° C. If the treatment temperature is too low, the reactivity is low, and the reforming with air is not performed sufficiently. On the other hand, if the temperature is too high, thermal polymerization of the pitch or tar itself occurs, and the reforming by air is not effectively performed. The air flow rate varies depending on the device shape, etc.
It is about 50 ml / g. At this time, use of a mesh or a filter or stirring may be applied to increase the contact efficiency between the pitch or tar and the air. Since the end point of the reforming by air involves an increase in the softening point, it can be determined by measuring the softening point. Although the softening point at the end point of the reforming cannot be specified by the starting material or the like, it is 150 to 350.
° C, preferably 200 to 300 ° C. Further, the atomic ratio of hydrogen to carbon is 0.50 to 0.80, and FT-IR
It is preferable that the ratio of the absorption intensity of the aliphatic CH stretching vibration measured in the above to the absorption intensity of the aromatic CH stretching vibration is 0.5 or more.

For the infusibilization treatment, compounds containing nitrogen, sulfur, oxygen and the like can be used. For example, nitric acid, sulfuric acid, a nitrating agent, a nitro compound, ammonium sulfate, ammonium acid sulfate, nitrogen dioxide gas, ozone, air, oxygen and the like, and a mixture thereof can be mentioned. Among them, the use of an oxidizing gas such as air is simple and inexpensive, and it is preferable in terms of the performance of the obtained carbon material that the amount of impurities remaining after firing is small. In particular, it is more preferable to use air gas because it is simple and inexpensive. The method of infusibilization with an oxidizing gas is not particularly limited, but after processing the modified pitch or tar into powder, fibrous, or thin film ground to a certain particle size or less, a temperature range of 100 to 400 ° C, preferably It is performed by flowing an oxidizing gas in a temperature range of 150 to 350 ° C. The step of infusibilizing the pitch or tar with an oxidizing gas is a method generally used in the production of carbon fiber and the like, and the higher the reactivity of pitch or tar to oxygen, the lower the temperature and the shorter the time. It is important for improving productivity. Here, it is considered that the methyl groups contained in the precursor pitch or tar and the modified pitch or tar, which are described in the present invention, improve the infusibility of the pitch or tar. Therefore, as can be seen from a comparison between Examples and Comparative Examples described later, by using a condensed polycyclic compound having a methyl group as a precursor pitch or tar raw material, a condensed polycyclic compound having no methyl group can be obtained. Infusibility can be achieved more quickly and under a condition with less heat history as compared with the case where it is used.

The raw material organic compound thus obtained is calcined under a non-oxidizing gas or under vacuum to obtain the carbon material of the present invention. Firing temperature is 800 ~ 1800
° C, preferably 1000-1300 ° C, firing time is 1 ~
In 50 hours, optimal conditions are appropriately selected according to the starting organic compound. Further, preliminary firing may be performed at 800 ° C. or lower. Nitrogen and argon are preferable as the non-oxidizing gas. A method in which a non-oxidizing gas is continuously supplied as an air stream and a gas generated by baking the raw material organic compound is discharged together with the gas, or a method in which the generated gas is forcibly discharged to the outside by evacuation can be appropriately applied. .

The carbon material for a negative electrode of a non-aqueous solvent-based secondary battery according to the present invention is characterized in that, in the production process thereof, the modified pitch or tar is excellent in infusibility with an oxidizing gas, and the potential for lithium metal potential is high. Between 0 and 1.5 V
A discharge capacity of 0 mAh / g or more is possible, and a capacity between 0 and 0.2 V with respect to lithium metal potential is 380 m
The most characteristic feature is that the irreversible capacity in the first cycle is 100 mAh / g or less. EXAMPLES Hereinafter, the effects of the present invention will be described specifically and in detail with reference to examples. However, the following examples are for the purpose of specifically describing the present invention and limit the embodiments and the scope of the present invention. It is not intended to do so. Also,
The pitch analysis method and analysis conditions in this embodiment are described below.

(Elemental analysis) For simultaneous analysis of carbon, nitrogen and hydrogen, PEKINELMER is used as an analyzer.
A 2400 CHN elemental analyzer manufactured by Sharp Corporation was used. The measurement is
1.5 ± 0.2 mg of the pitch of the sample was weighed in a tin container, set in the apparatus, burned at a temperature of 975 ° C. for 5 minutes, and detected and measured by TCD using a He gas carrier. Before measuring the sample, the standard substance acetanilide (2.
0 ± 0.1 mg).

(NMR Analysis) The ¹ H-NMR method was used to determine the proportion of aliphatic hydrogen in the total hydrogen contained in the precursor pitch or tar. Since almost all the pitch or tar is soluble in chloroform, a 1% deuterated chloroform solution was put into an NMR sample tube, and the measurement was performed using JNM-EX270 manufactured by JEOL Ltd. TMS (tetramethylsilane) is used as a reference material and
pm.

(FT-IR analysis) To 100 parts of KBr powder, 1 part of modified pitch or tar powder was added and mixed in an agate mortar. Then, I changed this to JASCO Corporation
FT / IR-5300, diffuse reflection measuring device DR-8
It was set to 1 and the measurement was performed. The peak intensity around 2930 cm ^-1 (the absorption intensity of aliphatic CH stretching vibration) and the peak intensity around 3050 cm ^-1 (the absorption intensity of aliphatic CH stretching vibration) on the spectrum obtained by subjecting the obtained diffuse reflection spectrum to Kubelka-Munk conversion. The ratio to the aromatic CH stretching force (absorption intensity) was determined.

Example 1 A 3 L acid-resistant autoclave was charged with 7 mol of methylnaphthalene, 3.68 mol of hydrogen fluoride (HF), and 1.16 mol of boron trifluoride (BF ₃ ) at 100 ° C. under autogenous pressure.
After the temperature was raised to 100 ° C., the reaction was continued for another 4 hours. Next, HF and BF ₃ were recovered by blowing nitrogen into the autoclave according to a conventional method, followed by removing low-boiling components to obtain a precursor pitch having a softening point of 76 ° C.
The ratio (H / C) of hydrogen atoms to carbon atoms contained in the precursor pitch is 0.87, and the pyridine-insoluble content is 0.0
%, And the proportion of aliphatic hydrogen in the total hydrogen contained in the pitch was 58%. The obtained precursor pitch was charged into another autoclave, and at a temperature of 320 ° C., 2 L / min.
Was blown in, and reacted for 2 hours to obtain a modified pitch having a softening point of 200 ° C. The ratio (H / C) of hydrogen atoms to carbon atoms contained in the modified pitch is 0.66, and FT−
The ratio of the absorption intensity of the aliphatic CH stretching vibration measured by IR to the absorption intensity of the aromatic CH stretching vibration was 1.1. This modified pitch is pulverized into powder having a size of 200 μm or less, and the temperature is raised from 150 ° C. to 300 ° C. at 5 ° C./min.
Hold for minutes and remove. The obtained treated material was adjusted to an average particle size of 15 μm, and then calcined at 1200 ° C. for 2 hours under a reduced pressure of 10 Torr while flowing a small amount of nitrogen to obtain a powdery carbon material.

(Evaluation as negative electrode material) 10 parts by weight of polyvinylidene fluoride powder (binder) was added to 90 parts by weight of the obtained carbon material, and the mixture was mixed and mixed with dimethylformamide as a solvent, and then applied on a copper foil. 1cm after drying
It was cut into a corner to obtain a test piece for evaluation. Then, LiC
The mixing ratio of 104 to ethylene carbonate / dimethyl carbonate / diethyl carbonate is 1 / 0.5 / 0.
5 dissolved in three kinds of mixture (concentration 1.0 mol / l
) Was used as an electrolyte to prepare a half cell using a 50 μm-thick polypropylene microporous membrane as a separator. Note that lithium metal having a diameter of 16 mm and a thickness of 0.5 mm was used as a counter electrode. A small piece of lithium metal was used as a reference electrode in the same manner as the counter electrode.

At a current density of ² mA / cm ² , a constant current charge was performed until the electrode potential of the test piece with respect to the reference electrode was 1 mV, and a constant potential charge was performed at an electrode potential of 1 mV for 40 hours. The occlusion capacity was 647 mAh / g. Was confirmed.
Next, when constant current discharge was performed at a current density of 1 mAh / cm ³ until the electrode potential of the test piece for evaluation with respect to the reference electrode was 1.5 V, a discharge capacity of 562 mAh / g was confirmed.
The capacity loss was 85 mAh / g, and the discharge capacity between 0 and 0.2 V with respect to the lithium metal potential was 417 mAh / g.

Example 2 A 3 L acid-resistant autoclave was charged with 7 mol of dimethylnaphthalene, 4.90 mol of hydrogen fluoride (HF) and 1.40 mol of boron trifluoride (BF ₃ ).
After the temperature was raised to 120 ° C., the reaction was continued for another 4 hours while maintaining the temperature at 120 ° C. Next, according to a conventional method, nitrogen was blown into the autoclave to recover HF and BF3. Subsequently, low boiling components were removed to obtain a precursor pitch having a softening point of 40 ° C.
The ratio (H / C) of hydrogen atoms to carbon atoms contained in the precursor pitch is 0.91, and the pyridine-insoluble content is 0.0
%, And the proportion of aliphatic hydrogen in the total hydrogen contained in the pitch was 66%. The obtained precursor pitch was charged into another autoclave, and at a temperature of 320 ° C., 2 L / min.
And reacted for 2 hours to obtain a 100% optically isotropic modified pitch having a softening point of 249 ° C. The ratio of hydrogen atoms to carbon atoms contained in the modified pitch (H /
C) was 0.65, and the ratio of the absorption intensity of aliphatic CH stretching vibration measured by FT-IR to the absorption intensity of aromatic CH stretching vibration was 1.6. This modified pitch is 200
Pulverize to a powder of μm or less, put 10 g into a porcelain dish, raise the temperature from 150 ° C. to 300 ° C. at a rate of 5 ° C./min. Was. The obtained treated product was adjusted to an average particle size of 15 μm, and then 10 Torr while flowing a small amount of nitrogen.
The powder was calcined at 1200 ° C. for 2 hours under reduced pressure to obtain a powdery carbon material. When the same negative electrode material was evaluated as in Example 1, an occlusion capacity of 635 mAh / g and an emission capacity of 547 mAh / g were confirmed. Capacity loss is 88
mAh / g, and 0 to 0.2 V with respect to lithium metal potential.
During this period was 397 mAh / g.

Example 3 142 g of ethylene bottom oil (manufactured by Maruzen Petrochemical) and hydrogen fluoride (HF) were placed in an acid-resistant autoclave having an inner volume of 3 L.
5.30 mol and 1.50 mol of boron trifluoride (BF ₃ ) were charged, and the temperature was raised to 120 ° C. under autogenous pressure, and the reaction was further maintained at 120 ° C. for 4 hours. Then, according to a conventional method, nitrogen is blown into the autoclave to form HF and B.
The F ₃ was recovered, and subsequently the low boiling components were removed to obtain a precursor pitch having a softening point of 107 ° C. The ratio (H / C) of hydrogen atoms to carbon atoms contained in the precursor pitch is 0.9.
5. The pyridine-insoluble content was 0.0%, and the proportion of aliphatic hydrogen in the total hydrogen contained in the pitch was 66%. The obtained precursor pitch was charged into another autoclave, and 340 ° C.
Then, 2 L of air was blown per minute per 100 g, and the mixture was reacted for 2 hours to obtain a 100% optically isotropic modified pitch having a softening point of 246 ° C. The ratio (H / C) of hydrogen atoms to carbon atoms contained in the modified pitch is 0.78, FT-I
The ratio of the absorption intensity of the aliphatic CH stretching vibration measured by R to the absorption intensity of the aromatic CH stretching vibration was 2.9. This modified pitch is pulverized into powder of 200 μm or less,
Put 10 g in a porcelain dish and air in a muffle furnace at 1 minute per minute.
While flowing L, the temperature was raised from 150 ° C. to 280 ° C. at 5 ° C./min, and then held for 10 minutes and taken out. The obtained treated material was adjusted to an average particle size of 15 μm, and then passed at 1200 ° C. under a reduced pressure of 10 Torr while flowing a small amount of nitrogen.
After firing for a time, a powdery carbon material was obtained. When an evaluation as a negative electrode material was performed in the same manner as in Example 1, the occlusion capacity:
658 mAh / g and a release capacity of 600 mAh / g were confirmed. The capacity loss is 58 mAh / g, and the discharge capacity between 0 and 0.2 V with respect to the lithium metal potential is 429 m.
Ah / g.

Comparative Example 1 The softening point was 76 ° C., the ratio of hydrogen atoms contained in the pitch to carbon atoms (H / C) was 0.55, the pyridine-insoluble content was 0.1%, and the total hydrogen contained in the pitch was A coal tar pitch containing 3% of aliphatic hydrogen therein was charged into an autoclave, and 2 l / min of air was blown per minute at 100 ° C. at 340 ° C. to react for 1 hour.
A 00% optically isotropic modified pitch was obtained. The ratio of hydrogen atoms to carbon atoms contained in the modified pitch (H /
C) was 0.48, and the ratio of the absorption intensity of the aliphatic CH stretching vibration measured by FT-IR to the absorption intensity of the aromatic CH stretching vibration was 0.0. This modified pitch is 200
Pulverize to a powder of μm or less, put 10 g in a porcelain dish, raise the temperature from 150 ° C. to 320 ° C. at a rate of 5 ° C./min. Was. The obtained processed product was melted in the process of raising the temperature and was in a lump. This was prepared into a powder having an average particle size of 15 μm,
Then, the mixture was calcined at 1200 ° C. for 2 hours under a reduced pressure of 10 Torr while flowing a small amount of nitrogen to obtain a powdery carbon material. When the same negative electrode material was evaluated as in Example 1, an occlusion capacity of 525 mAh / g and an emission capacity of 398 mAh / g were confirmed. Capacity loss is 127
mAh / g, and the charge / discharge capacity also decreased. Discharge capacity between 0 and 0.2 V with respect to lithium metal potential is 230 mA
h / g.

Comparative Example 2 In an acid-resistant autoclave having an inner volume of 3 L, 7 mol of naphthalene, 2.45 mol of hydrogen fluoride (HF) and boron trifluoride (BF) were added.
₃ ) After charging 0.77 mol, the temperature was raised to 100 ° C. under autogenous pressure, and the mixture was further reacted at 100 ° C. for 4 hours. Next, HF and BF ₃ were recovered by blowing nitrogen into the autoclave according to a conventional method, followed by removing low boiling components to obtain a precursor pitch having a softening point of 82 ° C. The ratio (H / C) of hydrogen atoms to carbon atoms contained in the precursor pitch is 0.76, the pyridine-insoluble content is 0.0%, and the proportion of aliphatic hydrogen in the total hydrogen contained in the pitch is 35%.
Met. The obtained precursor pitch was charged into another autoclave, and air was blown at 2 L / min at 340 ° C. per 100 g and reacted for 4 hours.
% Modified pitch with optical isotropy was obtained. The ratio (H / C) of hydrogen atoms to carbon atoms contained in the modified pitch is 0.49, and aromatic CH stretching vibration of absorption intensity of aliphatic CH stretching vibration measured by FT-IR. Was 0.20 with respect to the absorption intensity. This modified pitch is 200 μm
Pulverize to the following powder, put 10 g in a porcelain dish, and let air flow at 1 L / min in a muffle furnace.
The temperature was raised to 320 ° C./min. The obtained processed product was melted in the process of raising the temperature and was in a lump. This was prepared into a powder having an average particle diameter of 15 μm, and then calcined at 1200 ° C. for 2 hours under a reduced pressure of 10 Torr while flowing a small amount of nitrogen to obtain a powdery carbon material. When an evaluation as a negative electrode material was performed in the same manner as in Example 1, the occlusion capacity: 535 mAh / g, and the release capacity:
403 mAh / g was confirmed. 132mA capacity loss
h / g, and the charge / discharge capacity also decreased. The discharge capacity between 0 and 0.2 V with respect to the lithium metal potential is 240 mAh /
g and small.

[0023]

EFFECTS OF THE INVENTION Compared with the conventional carbon material for a negative electrode of a lithium secondary battery, a secondary battery having a large capacity and an inexpensive capacity is obtained because of its excellent productivity, large discharge capacity, and reduced irreversible capacity in the first cycle. Can be realized.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Joh Takahashi 22nd Wadai, Tsukuba, Ibaraki Prefecture Mitsubishi Gas Chemical Co., Ltd. Within the Research Institute (72) Inventor Norio Oishi 22nd Wadai, Tsukuba, Ibaraki Prefecture Mitsubishi Gas Chemical Co., Ltd. (72) Inventor Takaaki Higashiizumi 22nd Wadai, Tsukuba, Ibaraki Prefecture (72) Inventor Kyoko Shibahara 22nd Wadai, Tsukuba City, Ibaraki Prefecture Mitsubishi Gas Chemical Company, Ltd.

Claims (4)

[Claims] 1. A method for modifying a precursor pitch or tar obtained by polymerizing a condensed polycyclic compound containing one or more methyl groups or a substance containing the same in the presence of hydrogen fluoride / boron trifluoride. A method for producing a carbon material for a negative electrode of a non-aqueous solvent secondary battery, wherein the produced 100% optically isotropic modified pitch or tar is subjected to infusibilization treatment and then fired. 2. The softening point of the precursor pitch or tar is 0.
~ 180 ° C, the atomic ratio of hydrogen to carbon is 0.70
The non-aqueous solvent secondary battery negative electrode according to claim 1, wherein 1.10, a pyridine-insoluble content is 1.0% or less, and a ratio of aliphatic hydrogen to total hydrogen contained in pitch or tar is 30 to 80%. Manufacturing method of carbon material. 3. The modified pitch or tar has a softening point of 1
50 ° C. or more and 350 ° C. or less, the atomic ratio of hydrogen to carbon is 0.50 to 0.80, and aliphatic C- measured by FT-IR.
The method for producing a carbon material for a negative electrode of a non-aqueous solvent secondary battery according to claim 1, wherein the ratio of the absorption strength of the H stretching vibration to the absorption strength of the aromatic CH stretching vibration is 0.5 or more. 4. The non-aqueous solvent secondary according to claim 1, wherein the method of infusibilization treatment comprises treating pitch or tar at a temperature of 100 ° C. or more and 400 ° C. or less in the presence of an oxidizing gas. Manufacturing method of carbon material for battery negative electrode.