CN109888291A - Graphene applied to lithium ion battery adulterates conductive agent and its synthesis technology - Google Patents

Graphene applied to lithium ion battery adulterates conductive agent and its synthesis technology Download PDF

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CN109888291A
CN109888291A CN201910265579.7A CN201910265579A CN109888291A CN 109888291 A CN109888291 A CN 109888291A CN 201910265579 A CN201910265579 A CN 201910265579A CN 109888291 A CN109888291 A CN 109888291A
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graphene
added
carbon
conductive agent
lithium ion
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车春玲
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Shandong Xinghuo Science Technology Institute
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Shandong Xinghuo Science Technology Institute
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The present invention relates to a kind of graphenes applied to lithium ion battery to adulterate conductive agent and its synthesis technology, the following steps are included: the graphene oxide powder that (1) weighs 0.1g~0.5g is added in the deionized water of 10ml~50ml, tetra- water cobalt acetate of 0.5g~0.8g is added, i.e. acquisition Cobaltosic oxide/graphene catalyst.(2) 0.2g~0.5gCNT is weighed, 100ml~200mlN- methyl pyrrolidone is added, 1g~3g Cobaltosic oxide/graphene catalyst is added, ball milling mixing 2h~6h, heating obtains multi-layer graphene-carbon nanotubes particle under protective atmosphere.(3) mixed solvent for measuring ethyl alcohol and deionized water, is added the carbon nano-fiber of 0.5g~1g, and 0.2g~0.5g multi-layer graphene-carbon nanotubes particle is added, and drying obtains nano carbon fiber/graphite alkene/nanometer carbon pipe composite material.The unique two-dimensional structure of graphene can effectively form three-dimensional conductive network with carbon nano-fiber, carbon nanotubes in the present invention, and the maximized effect for playing conductive agent reduces the dosage of conductive agent, promotes lithium battery capacity.

Description

Graphene applied to lithium ion battery adulterates conductive agent and its synthesis technology
Technical field
The present invention relates to lithium battery material preparation fields, and in particular to a kind of graphene doping applied to lithium ion battery Conductive agent and its synthesis technology.
Background technique
With becoming more and more active for industrial development and mankind's activity, the mankind increase the consumption of the energy increasingly, and underground is non- Renewable resource is increasingly short, and energy supply and demand contradiction increasingly intensifies, and energy problem has become the pass for influencing human survival and development One of key problem.It is excellent that the lithium ion battery of new energy storage system should have that voltage is high, capacity is big, memory-less effect and service life are long etc. It is dynamic to can be widely applied to the digital products such as mobile phone, digital camera, laptop and electric vehicle, hybrid electric vehicle etc. for point Power tool.
Lithium ion battery is in charge and discharge cycles, when having electric current to pass through on positive and negative anodes pole piece, just has net reaction and occurs, table Prescribed electrode loses original equilibrium state, and electrode potential will deviate from equilibrium potential, just produces the polarization often said.Lithium battery pole Change can be divided into ohmic polarization, activation polarization and concentration polarization.Polarizing voltage is to react the important ginseng of internal electrochemical reaction Number will lead to cathode lithium metal and be precipitated and accelerate, can pierce through diaphragm under serious conditions causes if polarizing voltage is unreasonable for a long time Short circuit.According to lithium battery Initial Experimental Stage data, the simple electric conductivity for relying on active material is to be insufficient for electron transfer rate requirement , in order to enable electronics to fast move playback, there is the addition of conductive agent.The primary effect of conductive agent is to improve electronics electricity Conductance.Conductive agent plays the role of collecting micro-current between active substance, between active material and collector to reduce electricity The contact resistance of pole improves the migration rate of electronics in lithium battery, reduces battery polarization.In addition, conductive agent can also be improved pole Piece processability promotes infiltration of the electrolyte to pole piece, to improve the service life of lithium battery.Therefore, conductive agent is in lithium battery In play an important role and an indispensable component part of the industry.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provides a kind of graphene doping applied to lithium ion battery to lead Electric agent and its synthesis technology.
The technical solution adopted by the present invention to solve the technical problems is: a kind of graphene applied to lithium ion battery is mixed Miscellaneous conductive agent, including nano carbon fiber/graphite alkene/nanometer carbon pipe composite material.
A kind of synthesis technology of the graphene doping conductive agent applied to lithium ion battery, comprising the following steps:
(1) preparation of Cobaltosic oxide/graphene catalyst: the graphene oxide powder for weighing 0.1g~0.5g is added to In the deionized water of 10ml~50ml, it is ultrasonically treated 30min~60min, evenly dispersed graphene suspension is obtained, in solution Mixed solution after stirring 15min~30min, is poured into hydrothermal reaction kettle, mixed molten by middle tetra- water cobalt acetate of addition 0.5g~0.8g It is reacted 2h~5h hours at a temperature of 80 DEG C in a kettle~100 DEG C of liquid;
Then the mixing liquid after reaction is subjected to centrifugation 10min~30min, takes lower layer's particulate matter, using ethyl alcohol or steaming Distilled water cleans particulate matter, is subsequently placed in 60 DEG C~80 DEG C of drying case dry 20h~for 24 hours, that is, obtains four oxidations three Cobalt/graphen catalyst.
(2) multi-layer graphene-carbon nanotubes particle preparation: weighing 0.2g~0.5g carbon nanotube (CNT), is added In 100ml~200mlN- methyl pyrrolidone, 30~60min is stirred by ultrasonic, 1g~3g cobaltosic oxide/graphite is then added Then 30~60min is stirred by ultrasonic in alkene catalyst, ball milling mixing 2h~6h, form graphene/nanometer carbon pipe suspension;
Graphene/nanometer carbon pipe suspension is placed in quartz reaction kettle, in N2And C2H2Under duplicate protection atmosphere, heating To 500 DEG C~650 DEG C, 1h~2h is kept the temperature, i.e. acquisition multi-layer graphene-carbon nanotubes particle.
(3) it nano carbon fiber/graphite alkene/nanometer carbon pipe composite material preparation: measures 100ml~200ml ethyl alcohol and goes The carbon nano-fiber (VGCF) of 0.5g~1g is added in the mixed solvent of ionized water, after ultrasonic 1h~1.5h, prepares evenly dispersed Then 0.2g~0.5g multi-layer graphene-carbon nanotubes particle is added in carbon nano-fiber suspension, under room temperature, magnetic stirring 10h~12h hours, after being centrifuged 10min~30min, be placed in 500 DEG C~700 DEG C of vacuum drying oven dry 15h~ For 24 hours, nano carbon fiber/graphite alkene/nanometer carbon pipe composite material is obtained.
(4) alkene of nano carbon fiber/graphite made from/nanometer carbon pipe composite material can be used as a kind of doping of novel graphene and lead Electric agent good can be applied to lithium ion battery.
Further, the N2And C2H2Duplicate protection atmosphere refers to N2And C2H2Volume ratio be 3:1.
Further, the mixed solvent refers to that with ethyl alcohol and deionized water volume ratio be mixed solution made of 8:2.
The invention has the following advantages: graphene not only has high conductivity, but also its unique two wiener Rice structure extremely efficient can form three-dimensional conductive network with carbon nano-fiber, carbon nanotubes, can maximumlly play and lead The effect of electric agent reduces the dosage of conductive agent, so as to use active material, promotes lithium battery capacity more.
Specific embodiment
It is described in detail to various aspects of the present invention below, unless specific instructions, various raw materials of the invention can pass through It is prepared or is commercially available according to the conventional method of this field.
Embodiment 1
A kind of graphene doping conductive agent applied to lithium ion battery, including nano carbon fiber/graphite alkene/carbon nanotubes Composite material.
A kind of synthesis technology of the graphene doping conductive agent applied to lithium ion battery, comprising the following steps:
(1) preparation of Cobaltosic oxide/graphene catalyst: the graphene oxide powder for weighing 0.1g is added to 10ml's In deionized water, it is ultrasonically treated 30min, obtains evenly dispersed graphene suspension, tetra- water acetic acid of 0.5g is added in the solution Mixed solution after stirring 15min, is poured into hydrothermal reaction kettle by cobalt, and reaction 2h is small at a temperature of 80 DEG C in a kettle for mixed solution When;
Then the mixing liquid after reaction is subjected to centrifugation 10min, takes lower layer's particulate matter, using ethyl alcohol or distilled water to Grain object is cleaned, and dry 20h, i.e. acquisition Cobaltosic oxide/graphene catalyst are subsequently placed in 60 DEG C of drying case.
(2) multi-layer graphene-carbon nanotubes particle preparation: weighing 0.2g carbon nanotube (CNT), and 100mlN- first is added In base pyrrolidones, 30min is stirred by ultrasonic, then addition 1g Cobaltosic oxide/graphene catalyst, ball milling mixing 2h, then 30min is stirred by ultrasonic, forms graphene/nanometer carbon pipe suspension;
Graphene/nanometer carbon pipe suspension is placed in quartz reaction kettle, in N2And C2H2Under duplicate protection atmosphere, heating To 500 DEG C, 1h is kept the temperature, i.e. acquisition multi-layer graphene-carbon nanotubes particle.
(3) 100ml ethyl alcohol and deionized water nano carbon fiber/graphite alkene/nanometer carbon pipe composite material preparation: are measured Mixed solvent, is added the carbon nano-fiber (VGCF) of 0.5g, after ultrasonic 1h, prepares evenly dispersed carbon nano-fiber suspension, Then 0.2g multi-layer graphene-carbon nanotubes particle is added, under room temperature, magnetic stirs 10h hours, after being centrifuged 10min, It is placed in 500 DEG C of vacuum drying oven dry 15h, obtains nano carbon fiber/graphite alkene/nanometer carbon pipe composite material.
(4) alkene of nano carbon fiber/graphite made from/nanometer carbon pipe composite material can be used as a kind of doping of novel graphene and lead Electric agent good can be applied to lithium ion battery.
Further, the N2And C2H2Duplicate protection atmosphere refers to N2And C2H2Volume ratio be 3:1.
Further, the mixed solvent refers to that with ethyl alcohol and deionized water volume ratio be mixed solution made of 8:2.
Embodiment two
A kind of graphene doping conductive agent applied to lithium ion battery, including nano carbon fiber/graphite alkene/carbon nanotubes Composite material.
A kind of synthesis technology of the graphene doping conductive agent applied to lithium ion battery, comprising the following steps:
(1) preparation of Cobaltosic oxide/graphene catalyst: the graphene oxide powder for weighing 0.3g is added to 30ml's In deionized water, it is ultrasonically treated 50min, obtains evenly dispersed graphene suspension, tetra- water acetic acid of 0.7g is added in the solution Mixed solution after stirring 30min, is poured into hydrothermal reaction kettle by cobalt, and reaction 2h is small at a temperature of 100 DEG C in a kettle for mixed solution When;
Then the mixing liquid after reaction is subjected to centrifugation 20min, takes lower layer's particulate matter, using ethyl alcohol or distilled water to Grain object is cleaned, and dry 20h, i.e. acquisition Cobaltosic oxide/graphene catalyst are subsequently placed in 70 DEG C of drying case.
(2) multi-layer graphene-carbon nanotubes particle preparation: weighing 0.4g carbon nanotube (CNT), and 150mlN- first is added In base pyrrolidones, 45min is stirred by ultrasonic, then addition 2g Cobaltosic oxide/graphene catalyst, ball milling mixing 4h, then 45min is stirred by ultrasonic, forms graphene/nanometer carbon pipe suspension;
Graphene/nanometer carbon pipe suspension is placed in quartz reaction kettle, in N2And C2H2Under duplicate protection atmosphere, heating To 600 DEG C, 1.5h is kept the temperature, i.e. acquisition multi-layer graphene-carbon nanotubes particle.
(3) 150ml ethyl alcohol and deionized water nano carbon fiber/graphite alkene/nanometer carbon pipe composite material preparation: are measured Mixed solvent, is added the carbon nano-fiber (VGCF) of 0.8g, after ultrasonic 1h, prepares evenly dispersed carbon nano-fiber suspension, Then 0.4g multi-layer graphene-carbon nanotubes particle is added, under room temperature, magnetic stirs 10h hours, after being centrifuged 15min, It is placed in 600 DEG C of vacuum drying oven dry 20h, obtains nano carbon fiber/graphite alkene/nanometer carbon pipe composite material.
(4) alkene of nano carbon fiber/graphite made from/nanometer carbon pipe composite material can be used as a kind of doping of novel graphene and lead Electric agent good can be applied to lithium ion battery.
Further, the N2And C2H2Duplicate protection atmosphere refers to N2And C2H2Volume ratio be 3:1.
Further, the mixed solvent refers to that with ethyl alcohol and deionized water volume ratio be mixed solution made of 8:2.
Embodiment 3
A kind of graphene doping conductive agent applied to lithium ion battery, including nano carbon fiber/graphite alkene/carbon nanotubes Composite material.
A kind of synthesis technology of the graphene doping conductive agent applied to lithium ion battery, comprising the following steps:
(1) preparation of Cobaltosic oxide/graphene catalyst: the graphene oxide powder for weighing 0.5g is added to 50ml's In deionized water, it is ultrasonically treated 60min, obtains evenly dispersed graphene suspension, tetra- water acetic acid of 0.8g is added in the solution Mixed solution after stirring 30min, is poured into hydrothermal reaction kettle by cobalt, and reaction 5h is small at a temperature of 100 DEG C in a kettle for mixed solution When;
Then the mixing liquid after reaction is subjected to centrifugation 30min, takes lower layer's particulate matter, using ethyl alcohol or distilled water to Grain object is cleaned, and is subsequently placed in drying in 80 DEG C of drying case and for 24 hours, that is, is obtained Cobaltosic oxide/graphene catalyst.
(2) multi-layer graphene-carbon nanotubes particle preparation: weighing 0.5g carbon nanotube (CNT), and 200mlN- first is added In base pyrrolidones, 60min is stirred by ultrasonic, then addition 3g Cobaltosic oxide/graphene catalyst, ball milling mixing 6h, then 60min is stirred by ultrasonic, forms graphene/nanometer carbon pipe suspension;
Graphene/nanometer carbon pipe suspension is placed in quartz reaction kettle, in N2And C2H2Under duplicate protection atmosphere, heating To 650 DEG C, 2h is kept the temperature, i.e. acquisition multi-layer graphene-carbon nanotubes particle.
(3) 200ml ethyl alcohol and deionized water nano carbon fiber/graphite alkene/nanometer carbon pipe composite material preparation: are measured Mixed solvent, is added the carbon nano-fiber (VGCF) of 1g, after ultrasonic 1.5h, prepares evenly dispersed carbon nano-fiber suspension, Then 0.5g multi-layer graphene-carbon nanotubes particle is added, under room temperature, magnetic stirs 12h hours, after being centrifuged 30min, It is placed at drying in 700 DEG C of vacuum drying oven and for 24 hours, obtains nano carbon fiber/graphite alkene/nanometer carbon pipe composite material.
(4) alkene of nano carbon fiber/graphite made from/nanometer carbon pipe composite material can be used as a kind of doping of novel graphene and lead Electric agent good can be applied to lithium ion battery.
Further, the N2And C2H2Duplicate protection atmosphere refers to N2And C2H2Volume ratio be 3:1.
Further, the mixed solvent refers to that with ethyl alcohol and deionized water volume ratio be mixed solution made of 8:2.
The present invention is not limited to the embodiment, anyone should learn that the structure made under the inspiration of the present invention becomes Change, the technical schemes that are same or similar to the present invention are fallen within the scope of protection of the present invention.
Technology not described in detail in the present invention, shape, construction portion are well-known technique.

Claims (4)

1. a kind of graphene applied to lithium ion battery adulterates conductive agent, it is characterised in that: including nano carbon fiber/graphite Alkene/nanometer carbon pipe composite material.
2. a kind of synthesis technology of the graphene doping conductive agent applied to lithium ion battery, it is characterised in that: including following step It is rapid:
(1) preparation of Cobaltosic oxide/graphene catalyst: the graphene oxide powder for weighing 0.1g~0.5g is added to 10ml In the deionized water of~50ml, be ultrasonically treated 30min~60min, obtain evenly dispersed graphene suspension, in the solution plus Enter tetra- water cobalt acetate of 0.5g~0.8g, after stirring 15min~30min, mixed solution is poured into hydrothermal reaction kettle, mixed solution exists It is reacted 2h~5h hours at a temperature of 80 DEG C~100 DEG C in reaction kettle;
Then the mixing liquid after reaction is subjected to centrifugation 10min~30min, takes lower layer's particulate matter, using ethyl alcohol or distilled water Particulate matter is cleaned, dry 20h~for 24 hours, i.e. acquisition cobaltosic oxide/stone are subsequently placed in 60 DEG C~80 DEG C of drying case Black alkene catalyst;
(2) multi-layer graphene-carbon nanotubes particle preparation: weighing 0.2g~0.5g carbon nanotube (CNT), and addition 100ml~ In 200mlN- methyl pyrrolidone, 30~60min is stirred by ultrasonic, the catalysis of 1g~3g cobalt oxide/graphene is then added Then 30~60min is stirred by ultrasonic in agent, ball milling mixing 2h~6h, form graphene/nanometer carbon pipe suspension;
Graphene/nanometer carbon pipe suspension is placed in quartz reaction kettle, in N2And C2H2Under duplicate protection atmosphere, it is heated to 500 DEG C~650 DEG C, 1h~2h is kept the temperature, i.e. acquisition multi-layer graphene-carbon nanotubes particle;
(3) 100ml~200ml ethyl alcohol and deionization nano carbon fiber/graphite alkene/nanometer carbon pipe composite material preparation: are measured The carbon nano-fiber (VGCF) of 0.5g~1g is added in the mixed solvent of water, after ultrasonic 1h~1.5h, prepares evenly dispersed nanometer Then 0.2g~0.5g multi-layer graphene-carbon nanotubes particle is added in carbon fiber suspension, under room temperature, magnetic stirring 10h~ 12h hours, after being centrifuged 10min~30min, it is placed in 500 DEG C~700 DEG C of vacuum drying oven dry 15h~for 24 hours, is obtained To nano carbon fiber/graphite alkene/nanometer carbon pipe composite material;
(4) it is conductive that the alkene of nano carbon fiber/graphite made from/nanometer carbon pipe composite material can be used as a kind of novel graphene doping Agent good can be applied to lithium ion battery.
3. a kind of graphene applied to lithium ion battery according to claim 2 adulterates conductive agent and its synthesis technology, It is characterized by: the N2And C2H2Duplicate protection atmosphere refers to N2And C2H2Volume ratio be 3:1.
4. a kind of graphene applied to lithium ion battery according to claim 2 adulterates conductive agent and its synthesis technology, It is characterized by: the mixed solvent refers to that with ethyl alcohol and deionized water volume ratio be mixed solution made of 8:2.
CN201910265579.7A 2019-04-03 2019-04-03 Graphene applied to lithium ion battery adulterates conductive agent and its synthesis technology Withdrawn CN109888291A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112436139A (en) * 2019-08-24 2021-03-02 深圳格林德能源集团有限公司 Preparation method of three-dimensional composite conductive agent

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105036117A (en) * 2015-09-08 2015-11-11 杭州电子科技大学 Multilayer graphene and multi-walled carbon nanotube three-dimensional carbon material and preparation method thereof
CN109148887A (en) * 2018-08-30 2019-01-04 上海力信能源科技有限责任公司 A kind of production method of graphene-carbon nano-fiber conductive agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105036117A (en) * 2015-09-08 2015-11-11 杭州电子科技大学 Multilayer graphene and multi-walled carbon nanotube three-dimensional carbon material and preparation method thereof
CN109148887A (en) * 2018-08-30 2019-01-04 上海力信能源科技有限责任公司 A kind of production method of graphene-carbon nano-fiber conductive agent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112436139A (en) * 2019-08-24 2021-03-02 深圳格林德能源集团有限公司 Preparation method of three-dimensional composite conductive agent

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Application publication date: 20190614