CN105261734B - A kind of composite negative electrode material of lithium ion battery, preparation method and applications - Google Patents
A kind of composite negative electrode material of lithium ion battery, preparation method and applications Download PDFInfo
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- CN105261734B CN105261734B CN201510569923.3A CN201510569923A CN105261734B CN 105261734 B CN105261734 B CN 105261734B CN 201510569923 A CN201510569923 A CN 201510569923A CN 105261734 B CN105261734 B CN 105261734B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of composite negative electrode material of lithium ion battery, preparation method and applications.By Heteroatom doping, improve the capacity of burnt class soft carbon, meanwhile, by its with graphite material using mass ratio as 90~40:10~60 is compound, then coats organic matter pyrolytic carbon layer, and with reference to burnt class soft carbon high rate performance, the advantage that cycle performance is excellent and the first effect of graphite material is high, by simple cheap, environment-friendly process route, carbon/carbon compound cathode materials have been prepared.Negative material particle diameter D50=6.0~20.0 μm, specific surface area is 1.0~5.0m2/ g, compacted density are 1.0~1.5g/cm3, first coulombic efficiency bring up to more than 85%, circulate 500 capability retentions and be more than 90%, high rate performance lifting, 30C/1C capability retentions are more than 95%, available for lithium ion battery.
Description
Technical field
The invention belongs to lithium ion battery negative material field, is related to a kind of composite negative electrode material of lithium ion battery, system
Preparation Method and its application, in particular it relates to a kind of burnt class soft carbon composite negative pole material, preparation method and applications.
Background technology
Under the immense pressure of energy and environment problem, automobile industry searching clean energy resource, alternative energy source have undergone very long
Time.In recent years, in new-energy automobile multiple technologies route, " motorcar electric technology " shows one's talent, wherein lithium ion battery
As a research direction of most promising electrokinetic cell.
Negative material is the important component for influenceing performance of lithium ion battery.At present mainly using graphite as negative pole in industry
Material, still, as power battery electrode material, it is necessary to have excellent power-performance, cycle life and security performance.It is and single
Graphite material can not fully meet the requirement of above-mentioned power battery electrode material.
Soft carbon is due to its larger interlamellar spacing (d002), as lithium ion battery negative material, compared to graphite material, lithium
Ion wherein can quick deintercalation, there is excellent high rate performance；Simultaneously to electrolyte strong adaptability, overcharging resisting, cross and put, have
Excellent cycle life, so, soft carbon turns into the study hotspot of lithium ion battery cathode material.
CN103050699A discloses a kind of soft carbon negative electrode material of lithium ion battery and preparation method thereof, by the way that pitch is existed
Under catalyst action, carbonization thermal polycondensation obtains Carbonaceous mesophase bead, then obtains interphase by extracting drying, low-temperature carbonization
Microballoon soft carbon.Such soft carbon preparation technology is complicated, and cost is higher；Petroleum is burnt and coal measures Jiao is by carrying out coking to mink cell focus
Obtained amorphous carbon material, the raw material of lithium ion battery negative material artificial plumbago negative pole is widely used at present.By right
Petroleum is burnt or (800 DEG C~1500 DEG C) of coal measures Jiao low temperature is carbonized, and will obtain burnt class soft carbon material.CN103325997A、
CN103329320A, CN102428595A disclose the burnt class carbon material of low-temperature carbonization as negative material and its preparation side
Method, but capacity and first effect are relatively low.CN102428594A discloses burnt class carbon material and its preparation of a kind of phosphorus and boron codope
Method, although improving the capacity of burnt class soft carbon, it is single be used for power battery cathode material due to its average voltage it is higher,
Compacted density is low, causes energy density relatively low.CN103378357A discloses a kind of chargeable lithium electricity comprising soft carbon and graphite
Pond cathode composition, but the preparation method of soft carbon and graphite composite is not referred to.
The content of the invention
An object of the present invention is to provide a kind of composite negative electrode material of lithium ion battery, technical problems to be solved
It is reversible capacity, high rate performance and the cycle life for improving negative material, to applied to power lithium-ion battery.
To achieve these goals, present invention employs following technical scheme：
A kind of composite negative electrode material of lithium ion battery, the composite negative pole material include：
Component a；Or,
At least two combination in component a, b or c；
Wherein, component a, b and c independently has core shell structure, and component a is the compound of modified amorphous carbon and graphite
For kernel, amorphous carbon is the composite of clad；Component b is that modified amorphous carbon is kernel, and amorphous carbon is clad
Composite；Component c is that graphite is kernel, and amorphous carbon is the composite of clad.
In the present invention, amorphous carbon is modified, can be with the premise of its high rate performance and cycle performance are excellent
Improve the capacity of amorphous carbon.Graphite is added, using the advantage that the first effect of graphite material is high and compacted density is high, can be lifted non-
The compacted density of crystalloid carbon and first effect.Using amorphous carbon as clad, graphite and modified both amorphous carbons can be made more preferable
Combination.The present invention has obtained high capacity, compacted density height and high rate performance using the complex role between above-mentioned three
The excellent composite negative electrode material of lithium ion battery with cycle performance.
The typical but non-limiting composite negative electrode material of lithium ion battery of the present invention is as follows：
A kind of composite negative electrode material of lithium ion battery, the composite negative pole material include following components：Modified noncrystalline
The compound of carbon and graphite is kernel, and amorphous carbon is the composite of clad.
A kind of composite negative electrode material of lithium ion battery, the composite negative pole material include following components：Modified noncrystalline
The compound of carbon and graphite is kernel, and amorphous carbon is the composite of clad, and, modified amorphous carbon is kernel, without fixed
Shape carbon is the composite of clad.
A kind of composite negative electrode material of lithium ion battery, the composite negative pole material include following components：Modified noncrystalline
The compound of carbon and graphite is kernel, and amorphous carbon is the composite of clad, and, graphite is kernel, and amorphous carbon is bag
The composite of coating.
A kind of composite negative electrode material of lithium ion battery, the composite negative pole material include following components：Modified noncrystalline
Carbon is kernel, and amorphous carbon is the composite of clad, and, graphite is kernel, and amorphous carbon is the composite of clad.
A kind of composite negative electrode material of lithium ion battery, the composite negative pole material include following components：Modified noncrystalline
The compound of carbon and graphite is kernel, and amorphous carbon is the composite of clad, and, modified amorphous carbon is kernel, without fixed
Shape carbon is the composite of clad, and, graphite is kernel, and amorphous carbon is the composite of clad.
Preferably, the modified amorphous carbon is phosphorus doping soft carbon, preferably phosphorus doping Jiao class soft carbon, is more preferably
Phosphorus element content is 0.5~2.0wt% phosphorus doping Jiao's class soft carbon.The phosphorus element content is that 0.5~2.0wt% refers to, with phosphorus
The quality for adulterating burnt class soft carbon is 100wt%, and phosphorus element content is 0.5~2.0wt%.
Preferably, the raw material of burnt class soft carbon is petroleum green coke and/or coal measures green coke.Green coke (green coke) is by stone
Oil system or coal measures mink cell focus by modes such as delayed cokings, at a temperature of 400~700 DEG C or so thermal decomposition/polycondensation reaction obtain
Burnt class soft carbon material.Because treatment temperature is low, compared to calcined coke or calcined coke, the carbon-coating degree of order is low, and crystallinity is low, favorably
Reacted in hetero atom, form doped structure.Meanwhile green coke surface oxygen functional group is more rich, have more preferably with follow-up clad
Chemical interactions, more preferable covered effect can be formed.
Preferably, in composite negative pole material, the mass ratio of modified amorphous carbon and graphite is 90~40:10~60, example
Such as 90:10、85:15、80:20、60:40、50:50 or 40:60.
Preferably, the graphite is Delanium.Burnt class carbon material is presoma prepared by Delanium, from artificial stone
Black compound with burnt class soft carbon, obtained composite negative pole material can preferably be suitable for identical electrolyte system.
Preferably, the amorphous carbon is organic matter pyrolysis carbon, i.e., the presoma of described amorphous carbon is organic matter.Pass through
Using the amorphous carbon of organic matter pyrolysis as clad so that both graphite and phosphorus doping soft carbon preferably combine, organic matter heat
Solution carbon belongs to hard carbon material, compared to soft carbon material, interlamellar spacing (d002) bigger, high rate performance and to electrolyte better adaptability.
It as clad, on the one hand can further improve graphite and electrolyte adaptability, reduce solvent molecule insertion graphitic carbon
Expanded caused by layer, on the other hand can also stablize the stability of phosphorus doping soft carbon surface SEI films, so as to improve composite negative pole material
The cyclical stability of material.
Preferably, the amorphous carbon presoma is organic matter precursor, preferably citric acid, glucose, sucrose, poly- second
Glycol, epoxy resin, phenolic resin, PEO, polyimides, polypyrrole, polyaniline, polytetrafluoroethylene (PTFE) or polyvinylidene fluoride
In alkene any one or at least two combination.
Preferably, in the composite negative pole material, the quality sum and amorphous carbon of modification amorphous carbon and graphite
The ratio of quality is 99~90:1~10, such as may be selected 99:1、95:5、93:7 or 90:10, preferably 98~92:2~8.
Preferably, the average grain diameter of the composite negative pole material is D50=6.0~20.0 μm, for example, 7 μm, 9 μm, 11 μm,
13 μm, 15 μm, 17 μm or 19 μm, preferably average grain diameter is D50=10.0~15.0 μm.
Preferably, the specific surface area of the composite negative pole material is 1.0~5.0m2/ g, such as 1.5m2/g、2.0m2/g、
2.5m2/g、3.0m2/g、3.5m2/g、4.0m2/ g or 4.5m2/g。
Preferably, the powder body compacted density of the composite negative pole material is 1.0~1.5g/cm3, such as 1.05g/cm3、
1.1g/cm3、1.15g/cm3、1.20g/cm3、1.25g/cm3、1.30g/cm3、1.35g/cm3、1.40g/cm3Or 1.45g/cm3。
Preferably, the interlamellar spacing (d of the composite negative pole material002) it is 0.336~0.360nm.
Preferably, D peaks (~1360cm in the composite negative pole material Raman spectrum-1) and G peaks (~1580cm-1) average
Area ratio is 0.8~1.6；Wherein, D peaks (~1360cm in modified amorphous carbon (component A in Fig. 1) Raman spectrum-1) and G peaks
(~1580cm-1) average area ratio be 1.8~2.6；D peaks (~1360cm in graphite (B component in Fig. 1) Raman spectrum-1) and G
Peak (~1580cm-1) average area ratio be 0.1~0.6；D peaks (~1360cm in amorphous carbon (component C in Fig. 1) Raman spectrum-1) and G peaks (~1580cm-1) average area ratio be 1.8~3.0.
The typical but non-limiting technical scheme of the present invention is：
A kind of composite negative electrode material of lithium ion battery, the composite negative pole material are included in component a or component a, b or c
At least two combination, wherein, component a, b and c independently have a core shell structure, component a be phosphorus doping Jiao's class soft carbon with
The compound of graphite is kernel, and amorphous carbon is the composite of clad；Component b is that phosphorus doping Jiao's class soft carbon is kernel, nothing
Shape the composite that carbon is clad；Component c is that graphite is kernel, and amorphous carbon is the composite of clad, amorphous
The presoma of carbon is organic matter, and graphite is Delanium, and burnt class carbon material is presoma prepared by Delanium.
In the above-mentioned technical solutions, it is modified by single phosphorus doping, obtains high power capacity phosphorus doping Jiao's class soft carbon, adds stone
Ink, high using the first effect of graphite material, the high advantage of compacted density, the compacted density and head for improving phosphorus doping Jiao's class soft carbon is imitated.
In addition, burnt class carbon material is presoma prepared by Delanium, obtained Compound Negative compound from Delanium and burnt class soft carbon
Pole material can preferably be suitable for identical electrolyte system.Cladding is used as by the amorphous carbon of organic matter pyrolysis simultaneously
Layer so that both graphite and phosphorus doping Jiao's class soft carbon preferably combine.Organic matter pyrolysis carbon belongs to hard carbon material, compared to soft carbon
Material, interlamellar spacing (d002) is bigger, high rate performance and to electrolyte better adaptability, on the one hand can be with as clad
Further improve graphite and electrolyte adaptability, reduce and expanded caused by solvent molecule insertion graphite carbon-coating, on the other hand also may be used
To stablize the stability of phosphorus doping Jiao's class soft carbon surface SEI films, so as to improve the cyclical stability of composite negative pole material.Phosphorus doping
Burnt class soft carbon, graphite and organic matter pyrolysis carbon three have been compounded to form multiplying power and the excellent composite negative pole material of cycle performance.
The second object of the present invention is to provide a kind of preparation of composite negative electrode material of lithium ion battery as described above
Method, it the described method comprises the following steps：
The mixture and amorphous carbon presoma of modified amorphous carbon and graphite is dispersed in organic solvent, then
Dry, after end to be dried, carbonization treatment is carried out under inert atmosphere protection, obtains composite negative electrode material of lithium ion battery.
Preferably, the modified amorphous carbon is phosphorus doping soft carbon, preferably phosphorus doping Jiao class soft carbon, is more preferably
Phosphorus element content is 0.5~2.0wt% phosphorus doping Jiao's class soft carbon.
Preferably, the raw material of burnt class soft carbon is petroleum green coke and/or coal measures green coke.Green coke (green coke) is by stone
Oil system or coal measures mink cell focus by modes such as delayed cokings, at a temperature of 400~700 DEG C or so thermal decomposition/polycondensation reaction obtain
Burnt class soft carbon material.Because treatment temperature is low, compared to calcined coke or calcined coke, the carbon-coating degree of order is low, and crystallinity is low, favorably
Reacted in hetero atom, form doped structure.Meanwhile green coke surface oxygen functional group is more rich, have more preferably with follow-up clad
Chemical interactions, more preferable covered effect can be formed.
Preferably, the graphite is Delanium.Burnt class carbon material is presoma prepared by Delanium, from artificial stone
Black compound with burnt class soft carbon, obtained composite negative pole material can preferably be suitable for identical electrolyte system.
Preferably, the amorphous carbon presoma is organic matter precursor, preferably citric acid, glucose, sucrose, poly- second
Glycol, epoxy resin, phenolic resin, PEO, polyimides, polypyrrole, polyaniline, polytetrafluoroethylene (PTFE) or polyvinylidene fluoride
In alkene any one or at least two combination.By regarding the amorphous carbon of organic matter pyrolysis as clad so that stone
Ink and both phosphorus doping soft carbons preferably combine, and organic matter pyrolysis carbon belongs to hard carbon material, compared to soft carbon material, interlamellar spacing
(d002) bigger, high rate performance and to electrolyte better adaptability.As clad, it on the one hand can further improve stone
Ink and electrolyte adaptability, reduce and expanded caused by solvent molecule insertion graphite carbon-coating, on the other hand can also stablize phosphorus doping
The stability of soft carbon surface SEI films, so as to improve the cyclical stability of composite negative pole material.
Preferably, the organic solvent is any one in alcohols, ethers or esters or at least two combination.
Preferably, the mass ratio of the modified amorphous carbon and graphite is 90~40:10~60, such as 90:10、85:15、
80:20、60:40、50:50 or 40:60.
Preferably, the drying mode is any one in dry heating water bath, oil bath heating drying or spray drying.
Preferably, the quality sum of modified amorphous carbon and graphite and the ratio of the quality of amorphous carbon presoma for 98~
50:2~50, such as may be selected 90:10、85:15、80:20、75:25, preferably 95~70:5~30.
Preferably, under 500 DEG C~1200 DEG C (such as 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C or 1100 DEG C)
Carbonization treatment 0.5h~10h (such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9h), obtain lithium ion battery composite negative pole material
Material.
Preferably, the step of methods described after carbonization treatment also including being sieved.
Preferably, the preparation method of phosphorus doping Jiao class soft carbon is：
(a) raw material of burnt class soft carbon obtains the material powder of burnt class soft carbon by crushing and being classified；
(b) material powder of burnt class soft carbon is mixed with phosphorus-containing compound；
(c) mixture for obtaining step (b) under an inert atmosphere, carbonization treatment 0.5h at 500 DEG C~1500 DEG C~
10h, obtain phosphorus doping and be modified burnt class soft carbon.
Preferably, described in step (a) crush for ball milling, mechanical crushing, air-flow crushing or be sanded in any one or
The combination of person at least two, preferably air-flow crushing.
Preferably, sieve method, spiral-flow type classification, dry-type mechanical classification, dish-style classification or sleeping are classified as described in step (a)
Spiral shell formula classification in any one or at least two combination, preferably spiral-flow type be classified.
Preferably, in step (a) material powder of burnt class soft carbon average grain diameter be 0.5 μm~50 μm, preferably 5 μm~
30 μm, more preferably 8 μm~20 μm.
Preferably, phosphorus-containing compound described in step (b) is phosphoric acid and/or phosphate, preferably phosphoric acid, pyrophosphoric acid, phosphoric acid
In ammonium dihydrogen, diammonium hydrogen phosphate, sodium phosphate or magnesium phosphate any one or at least two combination.
Preferably, the mass ratio of the material powder of burnt class soft carbon and phosphorus-containing compound is 99~80 in step (b)：1~20,
Such as it may be selected 97:3、95:5,93:7、90:10、85:15、80:20 etc., preferably 99~90:1~10.
Preferably, inert atmosphere described in step (c) is any in nitrogen, argon gas, neon, helium, Krypton or xenon
It is a kind of or at least two combination, preferably nitrogen and/or argon gas.
Preferably, in step (c) carburizing temperature be 800 DEG C~1200 DEG C, such as may be selected 850 DEG C, 900 DEG C, 950 DEG C,
980 DEG C, 1050 DEG C or 1150 DEG C etc..
Preferably, carbonization time is 1h~5h in step (c), such as 1h, 1.5h, 2h, 3h or 4h etc. may be selected.
Preferably, the step with being well mixed is disperseed after carbonization treatment is also included in step (c).
Preferably, a kind of preparation method of composite negative electrode material of lithium ion battery, comprises the following steps：
(1) raw material of burnt class soft carbon is obtained into the burnt class soft carbon that average grain diameter is 0.5 μm~50 μm by crushing and being classified
Material powder；
(2) material powder of burnt class soft carbon is mixed with phosphorus-containing compound；
(3) mixture for obtaining step (2) under an inert atmosphere, carbonization treatment 0.5h at 500 DEG C~1500 DEG C~
10h, mixing break up to obtain phosphorus doping Jiao's class soft carbon；
(4) the phosphorus doping Jiao's class soft carbon for obtaining step (3) is 90~40 according to mass ratio with graphite:10~60 mixing are equal
It is even, obtain the mixture of phosphorus doping Jiao's class soft carbon and graphite；
(5) the phosphorus doping Jiao's class soft carbon and the mixture of graphite obtained step (4) is with amorphous carbon presoma according to matter
Measure ratio 95~50:5~50 it is dispersed then dry in organic solvent, after end to be dried, under inert atmosphere protection,
Carbonization treatment 0.5h~10h at 500 DEG C~1200 DEG C, composite negative electrode material of lithium ion battery is obtained after screening.
The third object of the present invention is to provide a kind of purposes of composite negative electrode material of lithium ion battery as described above,
It is used for lithium ion battery.
The present invention compared with prior art, has the advantages that：
(1) burnt class soft carbon raw material sources enrich, while cost is cheap；Miscellaneous original is adulterated by the mixing carbonization technique of simplicity
Son, the low deficiency of its capacity can be improved, burnt class soft carbon capacity is brought up into 300mAh/g~400mAh/g.This is due to hetero atom
Into carbon-coating so that the increase of the carbon-coating degree of disorder, so as to add more embedding lithium sites, be advantageous to the raising of capacity.
(2) the modification high power capacity Jiao's class soft carbon and graphite composite material of amorphous carbon layer cladding, first coulombic efficiency raising
To more than 85%, circulate 500 capability retentions and be more than 90%, high rate performance lifting, 30C/1C capability retentions are more than 95%.
On the one hand, simple burnt class soft carbon and graphite are compound, and the larger powder granule contact of particle diameter is not close, is coated by amorphous carbon,
So that the two combination is closer；On the other hand, graphite material causes expansion due to the insertion of electrolyte solvent molecule, cyclicity compared with
Difference, while P-O keys be present in phosphorus doping Jiao's class soft carbon, electrolyte lithium salt (such as LiPF can be caused6) decomposition, it is steady to reduce circulation
It is qualitative, by the cladding of amorphous carbon layer, prevent solvent molecule to be embedded in graphite carbon-coating, while also make the SEI on burnt class soft carbon surface
Film is more stable, so as to improve the cyclical stability of composite.
Brief description of the drawings
Fig. 1 is the burnt class soft carbon composite each component schematic diagram of the present invention, wherein, A is modified amorphous carbon, and B is graphite,
C is amorphous carbon.
Fig. 2 is the electromicroscopic photograph of the embodiment of the present invention 1.
Fig. 3 is the energy spectrum diagram of the embodiment of the present invention 1, wherein figure (a) is scanned picture, (b) is C element distribution map, (c) is
O distribution diagram of element, (d) are P element distribution map and (e) is energy spectrum diagram.
Fig. 4 is the XRD of the embodiment of the present invention 1.
Fig. 5 is the Raman spectrogram of the embodiment of the present invention 1, wherein figure (a) is Raman spectrogram, figure (b) is different tests
I (D)/I (G) area ratio of point.
Fig. 6 is the first charge-discharge curve map of the embodiment of the present invention 1.
Fig. 7 is the cycle performance figure of the embodiment of the present invention 1.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Physical index test of the present invention to composite in embodiment and comparative example characterizes equipment and test event such as table 1
It is shown.
Table 1 is composite physical index test event and corresponding test equipment
The present invention is as follows to the battery performance test of composite in embodiment and comparative example：
Using the soft carbon class negative material of the present invention, by negative material 90%~95%, binding agent 2%~5%, conductive agent
Negative pole is made in the mass ratio of 3%-~5%, and negative current collector uses copper foil.According to LiFePO490%~95%, binding agent 2%
~5%, positive pole is made in conductive agent 3%-5% mass ratio, and plus plate current-collecting body uses aluminium foil.The binding agent that positive and negative electrode uses for
Kynoar.Conductive agent is acetylene black.The electrolyte contained in electrolyte is electric conducting lithium salt LiPF6.Barrier film is
Celgard2400 type polypropylene diaphragms.Shell is organic material shell.
The making of negative plate：By the negative electrode active material of the present invention, acetylene black and it is dissolved in the poly- inclined of 1-METHYLPYRROLIDONE
PVF is according to mass ratio 90:5:5 are put into mixer, and required cathode size is obtained within 12 hours with 150 revs/min of stirrings.
Cathode size is put on tensile pulp machine, coated on 10 μm of copper foils, toasted 6 hours at 130 DEG C, in 10MPa pressure lower roll
Pressure, sheared according to 355mm × 43mm size, it is 100g/m to be fabricated to surface density2, compacted density 1.30g/cm3Negative pole
Piece.
The making of positive plate：By the LiFePO that average grain diameter is 2 μm4, acetylene black and be dissolved in the poly- of 1-METHYLPYRROLIDONE
Vinylidene is according to 91:5:4 mass ratio is put into mixer, is stirred 12 hours with 100 revs/min of mixing speeds.By positive pole
Slurry is put on tensile pulp machine, coated on 20 μm of aluminium foils, is toasted 6 hours at 150 DEG C, the roll-in under 25MPa pressure, according to
395mm × 42mm size shearing, is fabricated to surface density 200g/m2, compacted density 2.3g/cm3Anode pole piece.
The making of battery：Anode pole piece, Celgard2400 types polypropylene diaphragm and cathode pole piece are superimposed upon in sequence
Together, wind on the up- coiler of Shaoyang Dali Power Sources Co., Ltd. 053048, be fitted into after hot pressing in plastic casing.
Battery cell is put into baking box, vacuum bakeout 24 hours at 80 DEG C, then between battery cell is transferred to fluid injection, injection
1mol/L LiPF6EC+DMC (volume ratios 1:1) electrolyte, battery cell is fabricated to after sealing.
The test of battery：The battery cell that will be prepared, with the chemical conversion of 0.1C discharge and recharges 3 times, voltage range is 2.0~
3.65V, then with the capacity of Qingtian Industry Co., Ltd., Guangzhou's BS-8303Q battery test systems test battery cell, survey simultaneously
Try the high rate performance and cycle performance of battery cell.
Embodiment 1
Petroleum green coke raw material is classified to obtain particle diameter D by air-flow crushing and spiral-flow type50=8.0~10.0 microns of green coke
Powder, it is 97 according to mass ratio by green coke powder and ammonium dihydrogen phosphate:3, mixed with VC mixers, rotating speed 100r/min, mixing
30min, obtain mixture；Said mixture is placed in atmosphere furnace, nitrogen flow 120L/h, with 5 DEG C/min heating rate liters
Temperature is incubated 3h, obtains phosphorus doping Jiao's class soft carbon sample to 950 DEG C；By phosphorus doping Jiao's class soft carbon and D50=12 microns of artificial stone
Ink is 50 according to mass ratio:50, mixed with VC mixers, rotating speed 100r/min, mix 30min, obtained mixture and phenolic aldehyde
Resin is 90 according to mass ratio:10 disperse in alcohol solvent, stir, and mixture is placed in into atmosphere after heating water bath drying
In stove, nitrogen flow 120L/h, 950 DEG C are warming up to 5 DEG C/min heating rates, is incubated 3h, 200 eye mesh screens is crossed, obtains compound
Material.
As shown in Fig. 2 characterizing material morphology feature by ESEM, Quantitative Assessment of Particle Distribution is uniform.
As shown in figure 3, being characterized by power spectrum, it is containing C, O, P element, P element content in composite EDS spectrograms
0.87wt%；Element area profile can be seen that P element is uniformly distributed.
As shown in figure 4, in X ray diffracting spectrum, it can clearly be seen that graphite (002) characteristic peak in composite, meanwhile,
Nearby there is parcel peak at 25 °, from burnt class soft carbon and the diffraction maximum of organic matter pyrolysis carbon layer material.
As shown in figure 5, in Raman test spectrogram, choose 20 different sample spots and tested, average D peaks and G peak areas
Than for 1.309.
As shown in fig. 6, the first charge-discharge curve for being composite under 0.1C multiplying powers, first discharge specific capacity are
330mAh/g, coulombic efficiency 88%.
As shown in fig. 7, normal temperature 1C charge and discharge cycles, capability retention is 93% after 500 weeks.
Embodiment 2
Petroleum green coke raw material is classified to obtain particle diameter D by air-flow crushing and spiral-flow type50=9.0~15.0 microns of green coke
Powder, it is 95 according to mass ratio by green coke powder and ammonium dihydrogen phosphate:5, mixed with VC mixers, rotating speed 100r/min, mixing
30min, obtain mixture；Said mixture is placed in atmosphere furnace, nitrogen flow 120L/h, with 5 DEG C/min heating rate liters
Temperature is incubated 3h, obtains phosphorus doping Jiao's class soft carbon sample to 950 DEG C；By phosphorus doping Jiao's class soft carbon and D50=12 microns of natural stone
Ink is 50 according to mass ratio:50, mixed with VC mixers, rotating speed 100r/min, mix 30min, obtained mixture and epoxy
Resin is 80 according to mass ratio:20 disperse in isopropanol solvent, stir, and after oil bath heating is dried, mixture is placed in
In atmosphere furnace, nitrogen flow 120L/h, 950 DEG C are warming up to 5 DEG C/min heating rates, is incubated 3h, 200 eye mesh screens is crossed, obtains
Composite.
Embodiment 3
Petroleum green coke raw material is classified to obtain particle diameter D by air-flow crushing, spiral-flow type50=9.0~15.0 microns of green coke
Powder, it is 90 according to mass ratio by green coke powder and ammonium dihydrogen phosphate:10, mixed, rotating speed 100r/min, mixed with VC mixers
30min is closed, obtains mixture；Said mixture is placed in atmosphere furnace, nitrogen flow 120L/h, with 5 DEG C/min heating rates
800 DEG C are warming up to, 3h is incubated, obtains phosphorus doping Jiao's class soft carbon sample；By phosphorus doping Jiao's class soft carbon and D50=12 microns artificial
Graphite is 50 according to mass ratio:50, mixed with VC mixers, rotating speed 100r/min, mix 30min, obtained mixture and lemon
Lemon acid is 60 according to mass ratio:40 disperse in alcohol solvent, stir, mixture is placed in into atmosphere furnace after spray drying
In, nitrogen flow 120L/h, 1200 DEG C are warming up to 5 DEG C/min heating rates, is incubated 3h, 200 eye mesh screens is crossed, obtains composite wood
Material.
Embodiment 4
Coal measures green coke raw material is classified to obtain particle diameter D by air-flow crushing, spiral-flow type50=10.0~12.0 microns of coking powder
End, it is 95 according to mass ratio by green coke powder and sodium phosphate:5, mixed with VC mixers, rotating speed 100r/min, mix 30min,
Obtain mixture；Said mixture is placed in atmosphere furnace, nitrogen flow 120L/h, be warming up to 5 DEG C/min heating rates
1050 DEG C, 3h is incubated, obtains phosphorus doping Jiao's class soft carbon sample；By phosphorus doping Jiao's class soft carbon and D50=12 microns of Delanium is pressed
It is 60 according to mass ratio:40, mixed with VC mixers, rotating speed 100r/min, mix 30min, obtained mixture and polyethylene glycol
It is 85 according to mass ratio:15 disperse in alcohol solvent, stir, and mixture is placed in into atmosphere furnace after heating water bath drying
In, nitrogen flow 120L/h, 1050 DEG C are warming up to 5 DEG C/min heating rates, is incubated 3h, 200 eye mesh screens is crossed, obtains composite wood
Material.
Embodiment 5
Coal measures green coke raw material is classified to obtain particle diameter D by air-flow crushing, spiral-flow type50=10.0~12.0 microns of coking powder
End, it is 90 according to mass ratio by green coke powder and sodium phosphate:10, mixed with VC mixers, rotating speed 100r/min, mixing
30min, obtain mixture；Said mixture is placed in atmosphere furnace, nitrogen flow 120L/h, with 5 DEG C/min heating rate liters
Temperature is incubated 3h, obtains phosphorus doping Jiao's class soft carbon sample to 1050 DEG C；By phosphorus doping Jiao's class soft carbon and D50=12 microns of artificial stone
Ink is 60 according to mass ratio:40, mixed with VC mixers, rotating speed 100r/min, mix 30min, obtained mixture and sucrose
It is 80 according to mass ratio:20 disperse in alcohol solvent, stir, and mixture is placed in into atmosphere furnace after heating water bath drying
In, nitrogen flow 120L/h, 1050 DEG C are warming up to 5 DEG C/min heating rates, is incubated 3h, 200 eye mesh screens is crossed, obtains composite wood
Material.
Embodiment 6
Coal measures green coke raw material is classified to obtain particle diameter D by air-flow crushing, spiral-flow type50=10.0~12.0 microns of coking powder
End, it is 85 according to mass ratio by green coke powder and sodium phosphate:15, mixed with VC mixers, rotating speed 100r/min, mixing
30min, obtain mixture；Said mixture is placed in atmosphere furnace, nitrogen flow 120L/h, with 5 DEG C/min heating rate liters
Temperature is incubated 3h, obtains phosphorus doping Jiao's class soft carbon sample to 1050 DEG C；By phosphorus doping Jiao's class soft carbon and D50=12 microns of artificial stone
Ink is 60 according to mass ratio:40, mixed with VC mixers, rotating speed 100r/min, mix 30min, obtained mixture and polyphenyl
Amine is 90 according to mass ratio:10 disperse in alcohol solvent, stir, and mixture is placed in into atmosphere furnace after oil bath heating drying
In, nitrogen flow 120L/h, 1050 DEG C are warming up to 5 DEG C/min heating rates, is incubated 3h, 200 eye mesh screens is crossed, obtains composite wood
Material.
Comparative example 1
Petroleum green coke raw material is classified to obtain particle diameter D by air-flow crushing, spiral-flow type50=8.0~10.0 microns of green coke
Powder, it is placed in atmosphere furnace, nitrogen flow 120L/h, is warming up to 950 DEG C with 5 DEG C/min heating rates, is incubated 3h, burnt class soft carbon
Sample.
Comparative example 2
Petroleum green coke raw material is classified to obtain particle diameter D by air-flow crushing, spiral-flow type50=8.0~10.0 microns of green coke
Powder, it is 90 according to mass ratio by green coke powder and ammonium dihydrogen phosphate:10, mixed, rotating speed 100r/min, mixed with VC mixers
30min is closed, obtains mixture；Said mixture is placed in atmosphere furnace, nitrogen flow 120L/h, with 5 DEG C/min heating rates
950 DEG C are warming up to, 3h is incubated, obtains phosphorus doping Jiao's class soft carbon sample.
Comparative example 3
D50=12 microns of Delanium, is placed in atmosphere furnace, nitrogen flow 120L/h, with 5 DEG C/min heating rate liters
Temperature is incubated 3h, obtains comparative sample to 950 DEG C.
Comparative example 4
Petroleum green coke raw material is classified to obtain particle diameter D by air-flow crushing, spiral-flow type50=8.0~10.0 microns of green coke
Powder, it is 90 according to mass ratio by green coke powder and ammonium dihydrogen phosphate:10, mixed, rotating speed 100r/min, mixed with VC mixers
30min is closed, obtains mixture；Said mixture is placed in atmosphere furnace, nitrogen flow 120L/h, with 5 DEG C/min heating rates
950 DEG C are warming up to, 3h is incubated, obtains phosphorus doping Jiao's class soft carbon sample.By phosphorus doping Jiao's class soft carbon and D50=12 microns artificial
Graphite is 50 according to mass ratio:50, mixed with VC mixers, rotating speed 100r/min, mix 30min, it is soft to obtain phosphorus doping Jiao's class
The mixture of carbon and graphite.
Physical and chemical indexes test such as table 2 below.
Table 2
Battery performance test result such as table 3 below.
Table 3
From result above, adulterated by heteroatom phosphate, improve the specific capacity of burnt class soft carbon, meanwhile, by with stone
Ink is compound, improves the coulombic efficiency of burnt class soft carbon, is coated by amorphous carbon, obtained composite negative pole material has excellent
High rate performance and cyclical stability, available for automobile power lithium ion battery negative material.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (48)
1. a kind of composite negative electrode material of lithium ion battery, the composite negative pole material includes：
Component a；Or,
At least two combination in component a, b or c；
Wherein, component a, b and c independently has a core shell structure, and component a is that the compound of phosphorus doping Jiao's class soft carbon and graphite is
Kernel, amorphous carbon are the composite of clad；Component b is that phosphorus doping Jiao's class soft carbon is kernel, and amorphous carbon is clad
Composite；Component c is that graphite is kernel, and amorphous carbon is the composite of clad；
Phosphorus doping Jiao class soft carbon is prepared via a method which to obtain：
(a) raw material of burnt class soft carbon obtains the material powder of burnt class soft carbon by crushing and being classified；
(b) material powder of burnt class soft carbon is mixed with phosphorus-containing compound；
(c) mixture for obtaining step (b) under an inert atmosphere, carbonization treatment 0.5h~10h at 500 DEG C~1500 DEG C, obtains
Burnt class soft carbon is modified to phosphorus doping.
2. composite negative pole material as claimed in claim 1, it is characterised in that phosphorus doping Jiao class soft carbon is phosphorus element content
For 0.5~2.0wt% phosphorus doping Jiao's class soft carbon.
3. composite negative pole material as claimed in claim 1, it is characterised in that the raw material of burnt class soft carbon be petroleum green coke and/
Or coal measures green coke.
4. composite negative pole material as claimed in claim 1, it is characterised in that in composite negative pole material, phosphorus doping Jiao's class is soft
The mass ratio of carbon and graphite is 90~40:10~60.
5. composite negative pole material as claimed in claim 1, it is characterised in that the graphite is Delanium.
6. composite negative pole material as claimed in claim 1, it is characterised in that the presoma of the amorphous carbon is organic matter.
7. composite negative pole material as claimed in claim 6, it is characterised in that the presoma of the amorphous carbon be citric acid,
Glucose, sucrose, polyethylene glycol, epoxy resin, phenolic resin, PEO, polyimides, polypyrrole, polyaniline, poly- four
In PVF or Kynoar any one or at least two combination.
8. composite negative pole material as claimed in claim 1, it is characterised in that in the composite negative pole material, phosphorus doping is burnt
The ratio of the quality of the quality sum and amorphous carbon of class soft carbon and graphite is 99~90:1~10.
9. composite negative pole material as claimed in claim 8, it is characterised in that in the composite negative pole material, phosphorus doping is burnt
The ratio of the quality of the quality sum and amorphous carbon of class soft carbon and graphite is 98~92:2~8.
10. composite negative pole material as claimed in claim 1, it is characterised in that the average grain diameter of the composite negative pole material is
D50=6.0~20.0 μm.
11. composite negative pole material as claimed in claim 10, it is characterised in that the average grain diameter of the composite negative pole material is
D50=10.0~15.0 μm.
12. composite negative pole material as claimed in claim 1, it is characterised in that the specific surface area of the composite negative pole material is
1.0~5.0m2/g。
13. composite negative pole material as claimed in claim 1, it is characterised in that the powder-compacting of the composite negative pole material is close
Spend for 1.0~1.5g/cm3。
14. composite negative pole material as claimed in claim 1, it is characterised in that the interlamellar spacing (d of the composite negative pole material002)
For 0.336~0.360nm.
15. composite negative pole material as claimed in claim 1, it is characterised in that D peaks in the composite negative pole material Raman spectrum
(~1360cm-1) and G peaks (~1580cm-1) average area ratio be 0.8~1.6；Wherein, D in modified amorphous carbon Raman spectrum
Peak (~1360cm-1) and G peaks (~1580cm-1) average area ratio be 1.8~2.6；D peaks (~1360cm in graphite Raman spectrum-1) and G peaks (~1580cm-1) average area ratio be 0.1~0.6；D peaks (~1360cm in amorphous carbon Raman spectrum-1) and G peaks
(~1580cm-1) average area ratio be 1.8~3.0.
16. composite negative pole material as claimed in claim 1, it is characterised in that the composite negative pole material includes component a or group
At least two combination divided in a, b or c, wherein, component a, b and c independently have core shell structure, and component a is phosphorus doping
The compound of burnt class soft carbon and graphite is kernel, and amorphous carbon is the composite of clad；Component b is phosphorus doping Jiao's class soft carbon
For kernel, amorphous carbon is the composite of clad；Component c is that graphite is kernel, and amorphous carbon is the composite wood of clad
Material, the presoma of amorphous carbon is organic matter, and graphite is Delanium, and burnt class carbon material is presoma prepared by Delanium.
17. a kind of preparation method of composite negative electrode material of lithium ion battery as described in one of claim 1-16, including with
Lower step：
(I) phosphorus doping Jiao's class soft carbon is prepared as follows：
(a) raw material of burnt class soft carbon obtains the material powder of burnt class soft carbon by crushing and being classified；
(b) material powder of burnt class soft carbon is mixed with phosphorus-containing compound；
(c) mixture for obtaining step (b) under an inert atmosphere, carbonization treatment 0.5h~10h at 500 DEG C~1500 DEG C, obtains
Burnt class soft carbon is modified to phosphorus doping；
(II) composite negative pole material is prepared：
Dispersed in organic solvent, the Ran Hougan by the mixture of phosphorus doping Jiao's class soft carbon and graphite and amorphous carbon presoma
It is dry, after end to be dried, carbonization treatment is carried out under inert atmosphere protection, obtains composite negative electrode material of lithium ion battery.
18. method as claimed in claim 17, it is characterised in that phosphorus doping Jiao class soft carbon is that phosphorus element content is 0.5
~2.0wt% phosphorus doping Jiao's class soft carbon.
19. method as claimed in claim 17, it is characterised in that the raw material of burnt class soft carbon is petroleum green coke and/or coal measures
Green coke.
20. method as claimed in claim 17, it is characterised in that the graphite is Delanium.
21. method as claimed in claim 17, it is characterised in that the amorphous carbon presoma is organic matter precursor.
22. method as claimed in claim 21, it is characterised in that the amorphous carbon presoma is citric acid, glucose, sugarcane
Sugar, polyethylene glycol, epoxy resin, phenolic resin, PEO, polyimides, polypyrrole, polyaniline, polytetrafluoroethylene (PTFE) or
In Kynoar any one or at least two combination.
23. method as claimed in claim 17, it is characterised in that the organic solvent is appointing in alcohols, ethers or esters
Anticipate a kind of or at least two combinations.
24. method as claimed in claim 17, it is characterised in that the mass ratio of phosphorus doping Jiao class soft carbon and graphite is 90
~40:10~60.
25. method as claimed in claim 17, it is characterised in that the drying mode is heating water bath drying, oil bath heating
Dry or spray drying in any one.
26. method as claimed in claim 17, it is characterised in that phosphorus doping Jiao's class soft carbon and the quality sum of graphite with without fixed
The ratio of the quality of shape carbon matrix precursor is 98~50:2~50.
27. method as claimed in claim 26, it is characterised in that phosphorus doping Jiao's class soft carbon and the quality sum of graphite with without fixed
The ratio of the quality of shape carbon matrix precursor is 95~70:5~30.
28. method as claimed in claim 17, it is characterised in that carbonization treatment 0.5h~10h at 500 DEG C~1200 DEG C,
Obtain composite negative electrode material of lithium ion battery.
29. method as claimed in claim 28, it is characterised in that methods described also includes the step sieved after carbonization treatment
Suddenly.
30. method as claimed in claim 17, it is characterised in that the preparation method of phosphorus doping Jiao class soft carbon is：
(a) burnt class soft carbon raw material obtains burnt class soft carbon material powder by crushing and being classified；
(b) burnt class soft carbon material powder is mixed with phosphorus-containing compound；
(c) mixture for obtaining step (b) under an inert atmosphere, carbonization treatment 0.5h~10h at 500 DEG C~1500 DEG C, obtains
Burnt class soft carbon is modified to phosphorus doping.
31. method as claimed in claim 30, it is characterised in that crushed described in step (a) as ball milling, mechanical crushing, gas
Stream crush or be sanded in any one or at least two combination.
32. method as claimed in claim 31, it is characterised in that it is air-flow crushing to be crushed described in step (a).
33. method as claimed in claim 30, it is characterised in that sieve method, spiral-flow type point are classified as described in step (a)
Level, dry-type mechanical classification, dish-style classification or horizontal helical type classification in any one or at least two combination.
34. method as claimed in claim 33, it is characterised in that spiral-flow type classification is classified as described in step (a).
35. method as claimed in claim 30, it is characterised in that the average grain of the material powder of burnt class soft carbon in step (a)
Footpath is 0.5 μm~50 μm.
36. method as claimed in claim 35, it is characterised in that the average grain of the material powder of burnt class soft carbon in step (a)
Footpath is 5 μm~30 μm.
37. method as claimed in claim 36, it is characterised in that the average grain of the material powder of burnt class soft carbon in step (a)
Footpath is 8 μm~20 μm.
38. method as claimed in claim 30, it is characterised in that phosphorus-containing compound described in step (b) is phosphoric acid and/or phosphorus
Hydrochlorate.
39. method as claimed in claim 38, it is characterised in that phosphorus-containing compound described in step (b) is phosphoric acid, burnt phosphorus
In acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate or magnesium phosphate any one or at least two combination.
40. method as claimed in claim 30, it is characterised in that the material powder of burnt class soft carbon is with containing phosphatization in step (b)
The mass ratio of compound is 99~80：1~20.
41. method as claimed in claim 40, it is characterised in that the material powder of burnt class soft carbon is with containing phosphatization in step (b)
The mass ratio of compound is 99~90:1~10.
42. method as claimed in claim 30, it is characterised in that inert atmosphere described in step (c) is nitrogen, argon gas, neon
In gas, helium, Krypton or xenon any one or at least two combination.
43. method as claimed in claim 30, it is characterised in that inert atmosphere described in step (c) is nitrogen and/or argon
Gas.
44. method as claimed in claim 30, it is characterised in that carburizing temperature is 800 DEG C~1200 DEG C in step (c).
45. method as claimed in claim 30, it is characterised in that carbonization time is 1h~5h in step (c).
46. method as claimed in claim 30, it is characterised in that disperse after also including carbonization treatment in step (c) with mixing
Uniform step.
47. the method as described in one of claim 30-46, it is characterised in that comprise the following steps：
(1) raw material of burnt class soft carbon is obtained into the original for the burnt class soft carbon that average grain diameter is 0.5 μm~50 μm by crushing and being classified
Feed powder body；
(2) material powder of burnt class soft carbon is mixed with phosphorus-containing compound；
(3) mixture for obtaining step (2) under an inert atmosphere, carbonization treatment 0.5h~10h at 500 DEG C~1500 DEG C, mixes
Conjunction breaks up to obtain phosphorus doping Jiao's class soft carbon；
(4) the phosphorus doping Jiao's class soft carbon for obtaining step (3) is 90~40 according to mass ratio with graphite:10~60 is well mixed,
Obtain the mixture of phosphorus doping Jiao's class soft carbon and graphite；
(5) the phosphorus doping Jiao's class soft carbon and the mixture of graphite obtained step (4) is with amorphous carbon presoma according to mass ratio
95~50:5~50 it is dispersed then dry in organic solvent, after end to be dried, under inert atmosphere protection, 500 DEG C
Carbonization treatment 0.5h~10h at~1200 DEG C, composite negative electrode material of lithium ion battery is obtained after screening.
48. a kind of purposes of composite negative electrode material of lithium ion battery as described in one of claim 1-16, its be used for lithium from
Sub- battery.
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| CN111864206B (en) * | 2019-04-30 | 2023-11-03 | 贝特瑞新材料集团股份有限公司 | Hard carbon negative electrode material, preparation method thereof, pole piece containing hard carbon negative electrode material and lithium ion battery |
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| CN114628646A (en) * | 2020-12-11 | 2022-06-14 | 天津市贝特瑞新能源科技有限公司 | Composite negative electrode material, preparation method thereof and lithium ion battery |
| CN113206247A (en) * | 2021-03-19 | 2021-08-03 | 昆山宝创新能源科技有限公司 | Core-shell structure negative electrode material, preparation method thereof and lithium ion battery |
| CN114005973B (en) * | 2021-11-02 | 2023-05-12 | 贵州梅岭电源有限公司 | Preparation method and application of heteroatom modified composite anode material |
| CN114583107A (en) * | 2022-03-21 | 2022-06-03 | 珠海冠宇电池股份有限公司 | Battery with a battery cell |
| CN115440968A (en) * | 2022-06-24 | 2022-12-06 | 宁德新能源科技有限公司 | Negative electrode active material, secondary battery, and electronic device |
| CN115295759A (en) * | 2022-09-14 | 2022-11-04 | 江苏正力新能电池技术有限公司 | Negative pole piece and secondary battery |
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| CN102082272A (en) * | 2010-12-29 | 2011-06-01 | 长沙海容新材料有限公司 | Hard carbon coated lithium ion battery anode material and preparation method thereof |
| CN102208615B (en) * | 2011-05-05 | 2013-10-23 | 钱承亮 | Method for preparing carbon-carbon composite lithium ion battery cathode material |
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Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth, Patentee after: Beitrei New Materials Group Co.,Ltd. Address before: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth, Patentee before: Shenzhen BTR New Energy Materials Inc. |
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Effective date of registration: 20210910 Address after: 158100 leap forward Committee of Mashan District Central Community, Jixi City, Heilongjiang Province Patentee after: JIXI BTR GRAPHITE INDUSTRIAL PARK Co.,Ltd. Patentee after: Jixi Super Carbon Technology Co.,Ltd. Patentee after: Beitrei New Materials Group Co.,Ltd. Address before: 518106 Guangdong Shenzhen Guangming New District Gongming office, saitan community high tech Industrial Park eighth Patentee before: Beitrei New Materials Group Co.,Ltd. |
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Address after: 158100 leap forward Committee of Mashan District Central Community, Jixi City, Heilongjiang Province Patentee after: Jixi beiteri New Energy Technology Co.,Ltd. Patentee after: Jixi Super Carbon Technology Co.,Ltd. Patentee after: Beitrei New Materials Group Co.,Ltd. Address before: 158100 leap forward Committee of Mashan District Central Community, Jixi City, Heilongjiang Province Patentee before: JIXI BTR GRAPHITE INDUSTRIAL PARK Co.,Ltd. Patentee before: Jixi Super Carbon Technology Co.,Ltd. Patentee before: Beitrei New Materials Group Co.,Ltd. |
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