CN109004228A - The preparation method of lithium ion cell positive substrate - Google Patents

The preparation method of lithium ion cell positive substrate Download PDF

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Publication number
CN109004228A
CN109004228A CN201810874728.5A CN201810874728A CN109004228A CN 109004228 A CN109004228 A CN 109004228A CN 201810874728 A CN201810874728 A CN 201810874728A CN 109004228 A CN109004228 A CN 109004228A
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CN
China
Prior art keywords
graphene
lithium ion
preparation
ion cell
cell positive
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CN201810874728.5A
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Chinese (zh)
Inventor
黄进德
卢经纬
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Jiangsu Core Amperex Technology Ltd
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Jiangsu Core Amperex Technology Ltd
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Priority to CN201810874728.5A priority Critical patent/CN109004228A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • 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

Abstract

A kind of preparation method of lithium ion cell positive substrate provided by the invention, the preparation method is the following steps are included: graphene powder, graphene dispersion agent, solvent to be added in agitator tank with the ratio of mass ratio 5-8%:5-8%:84-90% and be stirred, it is uniformly mixed, obtains composite mortar;The composite mortar that will be stirred, is evenly applied to 12-16 μm of foil surface, and coating thickness is 2-3 μm;Foil after coating is compacted to 12-18 μm by roll squeezer;After compacting is completed, foil is toasted into 12-15h in vacuum oven, oven temperature is 40-50 DEG C to get arriving lithium ion cell positive substrate.The method of the present invention can greatly increase electric conductivity by addition graphene, reduce impedance, meanwhile, because the electric conductivity of graphene is higher than copper, copper foil foil thickness only needs the 60-80% of original thickness, can save the cost of 15-20%.

Description

The preparation method of lithium ion cell positive substrate
Technical field
The present invention relates to graphene combination electrode material fields, more particularly to the preparation side of lithium ion cell positive substrate Method.
Background technique
Lithium ion battery exists at present due to having many advantages, such as that discharge platform is high, energy density is big, having extended cycle life, environmental protection Power supply has become Major Members in the market.As petroleum fuel gradually reduces, environmental pollution is got worse and people are to environmental protection The enhancing of consciousness, people gradually attempt for lithium ion battery to be used for the fields such as pure electric automobile, hybrid-electric car.
However society above constantly spreads out of the message that lithium ion battery is on fire, explodes, and enables consumer to the peace of lithium ion battery Full performance generates query, and cycle performance is also to be improved.In order to improve security performance, high rate performance and the matter of lithium ion battery Specific energy is measured, scientific research personnel improves the performance of positive electrode by technologies such as doping, claddings, finds novel anode material to substitute Graphite type material used by existing lithium ion battery attempts production ceramic diaphragm material to improve breakdown characteristics, and trial-production is each Kind of high temperature resistant is not easily decomposed, the electrolyte of the characteristics such as overcharging resisting over-discharge, these technologies make lithium ion battery in safety and follow There is large increase on ring, but researcher is less to collector concern.
In lithium ion battery production at present, anode, as collector, is made using the aluminium foil with a thickness of 4-10 μm in high current With when, conveyance capacity will receive certain restrictions, and heat derives speed is general.
Summary of the invention
Technical problem: it is an object of the invention to solve prior art problem, a kind of lithium ion cell positive substrate is provided.
Technical solution: to achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of lithium ion cell positive substrate of the invention, the preparation method the following steps are included:
Step 1: by graphene powder, graphene dispersion agent, solvent with the ratio of mass ratio 5-8%:5-8%:84-90% Example, which is added in agitator tank, to be stirred, and is uniformly mixed, is obtained composite mortar;
Step 2: the composite mortar that will be stirred is evenly applied to 12-16 μm of foil surface, and coating thickness is 2-3 μm;
Step 3: the foil after step 2 is coated with is compacted to 12-18 μm by roll squeezer;
Step 4: after compacting is completed, foil is toasted into 12-15h in vacuum oven, oven temperature is 40-50 DEG C, i.e., Obtain lithium ion cell positive substrate.
Preferably, the graphene powder is made of sublevel graphene, and the sublevel graphene is by multilayer chip graphene Formed with diamond, the diamond is located between adjacent two layers of multilayer chip graphene, the diamond with it is described The carbon atom of multilayer chip graphene corresponds.
Preferably, the weight ratio of the multilayer chip graphene and the diamond is 18-19:1.
Preferably, the multilayer chip graphene is 3-5 lamellar graphene, every layer of the multilayer chip graphene With a thickness of 0.2-0.5nm;The interlamellar spacing of the adjacent two layers of the multilayer chip graphene is 0.2-0.4nm.
Preferably, the graphene dispersion agent is Emulsifier EL-60.
Preferably, solvent is deionized water.
Preferably, the foil is copper foil or aluminium foil.
Preferably, in the step 1, stirring condition are as follows: under vacuum conditions, temperature is 30-50 DEG C, and mixing speed is 50rpm, mixing time 8-10h.
Preferably, in the step 1 graphene powder, graphene dispersion agent, solvent mass ratio 5:5:90.
The utility model has the advantages that compared with prior art, the beneficial effects of the present invention are:
The present invention applies one layer of graphene on foil surface in advance, and grapheme material has good electric conductivity and thermal conductivity, and Copper foil requires conduction very harsh as battery plus plate current-collecting body, by adding graphene, can greatly increase electric conductivity, Impedance is reduced, therefore also largely reduces the calorific value in battery use process.Meanwhile because graphene electric conductivity Higher than copper, so copper thickness only needs the 60-80% of original thickness, the cost of 15-20% can be saved.
Detailed description of the invention
Fig. 1 is nominal 8Ah battery core 5C charge and discharge cycles figure (500 weeks).
Fig. 2 is nominal 8Ah battery core 5C charge and discharge discharge of electricity and temperature profile.
Fig. 3 is other battery core Life Cycle figures in the case of common material.
Specific embodiment
The embodiment of the present invention addressed below.The elements and features described in one embodiment of the invention can be with The elements and features shown in one or more other embodiments combine.It should be noted that for purposes of clarity, saying The expression and description of component unrelated to the invention, known to persons of ordinary skill in the art and processing are omitted in bright.
Heretofore described graphene powder is made of sublevel graphene, and the sublevel graphene is by multilayer chip graphene Formed with diamond, the diamond is located between adjacent two layers of multilayer chip graphene, the diamond with it is described The carbon atom of multilayer chip graphene corresponds;The weight ratio of the multilayer chip graphene and the diamond is 18-19: 1;The multilayer chip graphene is 3-5 lamellar graphene, every layer of the multilayer chip graphene with a thickness of 0.2- 0.5nm;The interlamellar spacing of the adjacent two layers of the multilayer chip graphene is 0.2-0.4nm;The diamond is Spherical Carbon, and institute The partial size for stating Spherical Carbon is 0.7-1.6nm.
Graphene powder used in the present invention, preparation method carry out in accordance with the following steps:
Step 1: preparing multilayer chip graphene using chemical deposition: with cathode-ray on silica substrate surface Deposit one layer of nickel metal layer.Cannot be other substrates, the nickel metal layer with a thickness of 200-400nm.
Step 2: be passed through in 950-1150 DEG C of temperature of tube furnace methane, hydrogen and ammonia composition gaseous mixture and Common graphite powder, and it is cooled to room temperature within the 100ms time, obtain multilayer chip graphene, multilayer chip graphite described herein The number of plies of alkene is 3-12 layers.
Step 3:, by being removed after electron microscope observation with molecular knife, being screened under 100,000 grades or more cleanliness environment 3-5 lamellar graphene out.
Step 4: the 3-5 lamellar graphene that step 3 filters out is mixed in proportion with diamond, it is evacuated to 100- 200MPa, temperature are controlled in 600-800 DEG C of stirring 36h, are prepared into graphene powder.
A kind of preparation method of lithium ion cell positive substrate of the invention, the preparation method the following steps are included:
Step 1: by graphene powder, graphene dispersion agent, solvent with the ratio of mass ratio 5-8%:5-8%:84-90% Example, which is added in agitator tank, to be stirred, and is uniformly mixed, is obtained composite mortar;
Step 2: the composite mortar that will be stirred is evenly applied to 12-16 μm of foil surface, and coating thickness is 2-3 μm;
Step 3: the foil after step 2 is coated with is compacted to 12-18 μm by roll squeezer;
Step 4: after compacting is completed, foil is toasted into 12-15h in vacuum oven, oven temperature is 40-50 DEG C, i.e., Obtain lithium ion cell positive substrate.
Embodiment 1
By 0.2g Graphene powder, 0.2g Emulsifier EL-60,2.4g deionized water is added in agitator tank;In vacuum item Under part, temperature is 30 DEG C, mixing speed 50rpm, mixing time 8h.The slurry that will be stirred uniformly is applied to 12 μm of copper Foil surface, 2 μm of coating thickness;13 μm are compacted to by roll squeezer after the completion of coating;After compacting is completed, in vacuum oven 12h is toasted, 50 DEG C of oven temperature, lithium ion cell positive substrate of the invention can be obtained.It is prepared into cylindrical LiFePO4 8Ah battery core.
Embodiment 2
By 0.6g Graphene powder, 0.6g Emulsifier EL-60,7.2g deionized water is added in agitator tank;In vacuum item Under part, temperature is 50 DEG C, mixing speed 50rpm, mixing time 8h.The slurry that will be stirred uniformly is applied to 16 μm of copper Foil surface, 3 μm of coating thickness;18 μm are compacted to by roll squeezer after the completion of coating;After compacting is completed, in vacuum oven 15h is toasted, 50 DEG C of oven temperature, lithium ion cell positive substrate of the invention can be obtained.It is prepared into cylindrical LiFePO4 21Ah battery core.
Embodiment 3
By 0.06g Graphene powder, 0.06g Emulsifier EL-60,0.72g deionized water is added in agitator tank;True Under empty condition, temperature is 50 DEG C, mixing speed 50rpm, mixing time 10h.The slurry that will be stirred, is uniformly applied to 14 μm copper foil surface, 2 μm of coating thickness;15 μm are compacted to by roll squeezer after the completion of coating;It is roasting in vacuum after compacting is completed 12h is toasted in case, and 50 DEG C of oven temperature, lithium ion cell positive substrate of the invention can be obtained.It is prepared into cylindrical ternary 2.2Ah battery core.
Charge and discharge cycles test analysis:
It is depressed in a normal atmosphere, in room temperature environment, carries out charge and discharge cycles test to cylindrical battery core is prepared into Analysis.Test battery core specification: 3.2V8Ah.
1: with 5C multiplying power (40A) constant-current charge to 3.65V, switching constant pressure 3.65V charges to electric current and is reduced to 0.01C (0.08A);2: standing 30 minutes;3: 2.5V is discharged to 5C multiplying power (40A);4: standing 30 minutes;5: repeating step 1-4.
Test result is as follows for charge and discharge cycles:
As shown in Figure 1, being the nominal 8Ah battery core of embodiment 1,5C charge and discharge cycles figure (500 weeks) is adding as can be seen from Figure After new material, cycle life decaying is faint, and charge conservation rate is powerful.
As shown in Fig. 2, being the nominal 8Ah battery core single charge and discharge of embodiment 1 and temperature curve, adding newly as can be seen from Figure After material, the more conventional battery core of temperature change is good many in the case of high power charging-discharging.
As shown in figure 3, being other common material battery core charge and discharge cycles figures, as can be seen from Figure, the positive material of same system In the case of material, service life decline is obvious after 1C charge and discharge, and produces irreversible damage after multiple circulation.
Graphene dispersion agent uses Emulsifier EL-60 in the present invention, can stable dispersion graphene, graphene leads Electrically also it is greatly improved.
The present invention applies one layer of graphene on foil surface in advance, and grapheme material has good electric conductivity and thermal conductivity, and Copper foil requires conduction very harsh as battery plus plate current-collecting body, by adding graphene, can greatly increase electric conductivity, Impedance is reduced, therefore also largely reduces the calorific value in battery use process.Meanwhile because graphene electric conductivity The cost of 15-20% can be saved so copper foil foil thickness only needs the 60-80% of original thickness higher than copper.
The above is merely a preferred embodiment of the present invention, it is noted that for those skilled in the art For, under the premise of not departing from core of the invention technology, improvements and modifications can also be made, these improvements and modifications are also answered Belong to scope of patent protection of the invention.With any change in the comparable meaning and scope of claims of the present invention, all It is considered as being included within the scope of the claims.

Claims (9)

1. a kind of preparation method of lithium ion cell positive substrate, which is characterized in that the preparation method the following steps are included:
Step 1: graphene powder, graphene dispersion agent, solvent are added to the ratio of mass ratio 5-8%:5-8%:84-90% It is stirred in agitator tank, is uniformly mixed, obtains composite mortar;
Step 2: the composite mortar that will be stirred is evenly applied to 12-16 μm of foil surface, and coating thickness is 2-3 μm;
Step 3: the foil after step 2 is coated with is compacted to 12-18 μm by roll squeezer;
Step 4: after compacting is completed, toasting 12-15h for foil in vacuum oven, and oven temperature is 40-50 DEG C to get arriving Lithium ion cell positive substrate.
2. the preparation method of lithium ion cell positive substrate according to claim 1, which is characterized in that the Graphene powder End is made of sublevel graphene, and the sublevel graphene is made of multilayer chip graphene and diamond, and the diamond is located at Between adjacent two layers of multilayer chip graphene, the carbon atom one of the diamond and the multilayer chip graphene is a pair of It answers.
3. the preparation method of lithium ion cell positive substrate according to claim 2, which is characterized in that the multilayer chip The weight ratio of graphene and the diamond is 18-19:1.
4. the preparation method of lithium ion cell positive substrate according to claim 1, which is characterized in that the multilayer chip Graphene is 3-5 lamellar graphene, every layer of the multilayer chip graphene with a thickness of 0.2-0.5nm;The multilayer tablet The interlamellar spacing of the adjacent two layers of shape graphene is 0.2-0.4nm.
5. the preparation method of lithium ion cell positive substrate according to claim 1, which is characterized in that the graphene point Powder is Emulsifier EL-60.
6. the preparation method of lithium ion cell positive substrate according to claim 1, which is characterized in that solvent is deionization Water.
7. the preparation method of lithium ion cell positive substrate according to claim 1, which is characterized in that the foil is copper Foil or aluminium foil.
8. the preparation method of lithium ion cell positive substrate according to claim 1, which is characterized in that the step 1 In, stirring condition are as follows: under vacuum conditions, temperature is 30-50 DEG C, mixing speed 50rpm, mixing time 8-10h.
9. the preparation method of lithium ion cell positive substrate according to claim 1, which is characterized in that in the step 1 Graphene powder, graphene dispersion agent, solvent mass ratio 5:5:90.
CN201810874728.5A 2018-08-03 2018-08-03 The preparation method of lithium ion cell positive substrate Pending CN109004228A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113640581A (en) * 2021-08-10 2021-11-12 常州第六元素材料科技股份有限公司 Graphene conductivity analysis method
CN116207374A (en) * 2023-05-04 2023-06-02 梅州市博富能科技有限公司 Water-based lithium ion battery and manufacturing method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103187576A (en) * 2011-12-28 2013-07-03 清华大学 Current collector, electrochemical battery electrode and electrochemical battery
CN103725046A (en) * 2012-10-12 2014-04-16 东丽先端材料研究开发(中国)有限公司 Graphene dispersion liquid and preparation method thereof
CN107445146A (en) * 2017-07-21 2017-12-08 昆山正国新能源动力电池有限公司 Lithium ion battery time layer graphene and preparation method
CN107482167A (en) * 2017-07-21 2017-12-15 昆山正国新能源动力电池有限公司 high temperature lithium cell positive pole and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103187576A (en) * 2011-12-28 2013-07-03 清华大学 Current collector, electrochemical battery electrode and electrochemical battery
CN103725046A (en) * 2012-10-12 2014-04-16 东丽先端材料研究开发(中国)有限公司 Graphene dispersion liquid and preparation method thereof
CN107445146A (en) * 2017-07-21 2017-12-08 昆山正国新能源动力电池有限公司 Lithium ion battery time layer graphene and preparation method
CN107482167A (en) * 2017-07-21 2017-12-15 昆山正国新能源动力电池有限公司 high temperature lithium cell positive pole and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113640581A (en) * 2021-08-10 2021-11-12 常州第六元素材料科技股份有限公司 Graphene conductivity analysis method
CN113640581B (en) * 2021-08-10 2023-12-15 常州第六元素材料科技股份有限公司 Graphene conductivity analysis method
CN116207374A (en) * 2023-05-04 2023-06-02 梅州市博富能科技有限公司 Water-based lithium ion battery and manufacturing method thereof
CN116207374B (en) * 2023-05-04 2023-11-24 梅州市博富能科技有限公司 Water-based lithium ion battery and manufacturing method thereof

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