CN103647040A - Electrode slurry, negative electrode and lithium ion battery using negative electrode - Google Patents

Electrode slurry, negative electrode and lithium ion battery using negative electrode Download PDF

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CN103647040A
CN103647040A CN201310560322.7A CN201310560322A CN103647040A CN 103647040 A CN103647040 A CN 103647040A CN 201310560322 A CN201310560322 A CN 201310560322A CN 103647040 A CN103647040 A CN 103647040A
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negative electrode
lithium ion
ion battery
electrode
carboxymethyl cellulose
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陈敬波
王要武
何向明
赵骁
方谋
徐盛明
李建军
王莉
高剑
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Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
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Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
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Priority to PCT/CN2014/089738 priority patent/WO2015070706A1/en
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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Abstract

The invention provides an electrode slurry, and a negative electrode used for manufacturing a lithium ion battery. The electrode slurry comprises manganese dioxide, butadiene styrene rubber, carboxymethyl cellulose, water, and a conductive agent. The negative electrode of a lithium ion battery comprises a negative electrode current collector and a negative electrode material layer attached to the surface of the negative electrode current collector; the negative electrode material layer comprises manganese dioxide, butadiene styrene rubber, carboxymethyl cellulose and a conductive agent. The lithium ion battery comprises a negative electrode, a positive electrode, and a non-aqueous electrolyte located between the positive electrode and the negative electrode; the negative electrode comprises a negative electrode current collector and a negative electrode material layer attached to the surface of the negative electrode current collector; the negative electrode material layer comprises manganese dioxide, butadiene styrene rubber, carboxymethyl cellulose and a conductive agent.

Description

Electrode slurry, negative electrode and apply the lithium ion battery of this negative electrode
Technical field
The present invention relates to a kind of electrode slurry, negative electrode and apply the lithium ion battery of this negative electrode.
Background technology
The business-like negative material of lithium ion battery adopts graphite mostly, but the theoretical lithium storage content of graphite material only has 372mAh/g.For meeting the demand of high-capacity lithium ion cell, the graphite cathode material of researching and developing the alternative current commercial applications of novel height ratio capacity lithium ion battery negative material seems very urgent and necessary.
Since people's reported first transition metal oxide (TMOs such as Poizot in 2000, transition metal oxides), as since lithium ion battery negative material, transition metal oxide and other transistion metal compounds (TMX) are quite concerned as lithium ion battery negative material.Transition metal oxide, as Fe, Ni, Co, Cu etc., generally has similar electrochemical behavior.Its removal lithium embedded mechanism is generally: during embedding lithium, Li is embedded in transition metal oxide, by displacement reaction, generates metal nanoparticle, and is evenly embedded in the Li of generation 2in O matrix; During de-lithium, reversible generation transition metal oxide and lithium again.
In these transition metal oxides, the oxide of manganese metal, as MnO, Mn 3o 4, Mn 2o 3, MnO 2deng, be widely used in all kinds of electrochemical energy storage equipment and excite wide spread interest.The oxide of manganese has numerous structures, and its electrochemical behavior depends on oxidation state, nanostructure and form strongly.According to theory, calculate MnO, Mn 3o 4, Mn 2o 3, MnO 2theory storage lithium specific capacity be respectively 755,936,1018,1232mAh/g.So MnO 2specific capacity the highest.Traditionally, MnO 2positive electrode as disposable lithium-battery in field of batteries is widely used, because its lower reversible capacity and poor cyclical stability cannot be applied to secondary lithium battery.
In recent years, due to MnO 2there is higher theoretical specific capacity, and abundant natural resources, to MnO 2research as lithium ion battery negative material has the trend increasing, yet, MnO 2chemical property far away cannot be satisfactory, and reversible specific capacity is lower first, and what more cannot make us accepting is cycle performance extreme difference, along with the increase battery capacity decay of cycle-index is rapid.Even there is researcher to suspect MnO 2whether there is electro-chemical activity, can be applied to secondary lithium battery.On the other hand, according to hydrophily, lithium ion battery binding agent used can be divided into two classes, and a class is organic solvent type binding agent, adopts organic solvent as dispersant, and a class is aqua type binding agent, adopts water as dispersant.At MnO 2the pole piece of negative electrode is made upper, and prior art adopts Kynoar (PVDF) as binding agent, adopts organic solvent as dispersant.Also do not see at present the report that adopts other binding agents.
In lithium ion battery, binding agent General Requirements Ohmic resistance is little, and stable at electrolyte performance, as caking property, pliability, hydrophily and alkali resistance etc., this has directly affected the performance of lithium ion battery.Select suitable binding agent to be related to whether can to obtain higher specific capacity, longer cycle life and lower internal resistance, and be conducive to improve high rate performance and the cryogenic property of battery.
Summary of the invention
In view of this, the necessary lithium ion battery that a kind of electrode slurry, negative electrode is provided and applies this negative electrode, this lithium ion battery has higher reversible specific capacity first and excellent cycle performance.
An electrode slurry, for making the negative electrode of lithium ion battery, comprises manganese dioxide, butadiene-styrene rubber, carboxymethyl cellulose, water and conductive agent.
A negative electrode for lithium ion battery, comprises negative current collector and is attached to the negative electrode material layer of this negative pole currect collecting surface, this negative electrode material layer comprises manganese dioxide, butadiene-styrene rubber, carboxymethyl cellulose and conductive agent.
A kind of lithium ion battery, comprise negative electrode, positive electrode and the nonaqueous electrolyte between this positive electrode and negative electrode, this negative electrode comprises negative current collector and is attached to the negative electrode material layer of this negative pole currect collecting surface, and this negative electrode material layer comprises manganese dioxide, butadiene-styrene rubber, carboxymethyl cellulose and conductive agent.
Compared to prior art, the invention provides a kind of lithium ion battery negative material MnO 2make electrode plates novel electrode binding agent used (or binder system, be referred to as binding agent below), comprise butadiene-styrene rubber and carboxymethyl cellulose, this binding agent and MnO 2can form good cooperation, contribute to lithium ion battery negative material MnO 2give play to higher reversible specific capacity first and demonstrated excellent cycle performance.
Accompanying drawing explanation
Fig. 1 is the negative active core-shell material MnO of the embodiment of the present invention 2charge and discharge cycles test curve.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments electrode slurry provided by the invention, negative electrode and the lithium ion battery of applying this negative electrode are described in further detail.
The embodiment of the present invention provides a kind of electrode slurry, for making the negative electrode of lithium ion battery, comprises manganese dioxide (MnO 2), butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC), water and conductive agent.
Particularly, this MnO 2for negative active core-shell material, SBR and CMC are binding agent, and water is solvent.Conductive agent, without particular restriction, can be conductive agent conventional in lithium ion battery negative electrode, as one or more in conductive carbon black, electrically conductive graphite, acetylene black, carbon fiber, carbon nano-tube, Graphene and graphite etc.
In this binding agent, CMC plays thickener, improves MnO in electrode slurry 2dispersion effect, SBR plays cementation, by MnO 2particle and MnO 2particle, together with conductive agent particle bond, and is attached on collection liquid surface.The chemical formula of SBR and CMC is as follows:
Figure 2013105603227100002DEST_PATH_IMAGE001
This binding agent comprises the combination of SBR and CMC, and the mass ratio between SBR and CMC is 1:5 ~ 5:1, and preferably, the mass ratio between SBR and CMC is 1:2 ~ 2:1.This MnO 2, conductive agent, SBR and the gross mass of CMC and the mass ratio of this water be preferably 1:5 ~ 5:1, is preferably 1:1 ~ 1:2, thereby can makes this electrode slurry have good rheological characteristic, be beneficial to and film.
At this MnO 2, in conductive agent, SBR and CMC, preferably, MnO 2quality account for 50% ~ 90% of gross mass, the quality of SBR accounts for 1% ~ 10% of gross mass, the quality of CMC accounts for 1% ~ 10% of gross mass.
The embodiment of the present invention further provides a kind of negative electrode, comprises negative current collector and is attached to the negative electrode material layer of this negative pole currect collecting surface.This negative current collector can be copper or nickel, but is not limited to copper and mickel.This negative electrode material layer comprises manganese dioxide, butadiene-styrene rubber, carboxymethyl cellulose and conductive agent.This negative electrode material layer is for being coated in above-mentioned electrode slurry negative pole currect collecting surface also except forming after anhydrating.In this negative electrode material layer, preferably, MnO 2quality account for 50% ~ 90% of gross mass, the quality of SBR accounts for 1% ~ 10% of gross mass, the quality of CMC accounts for 1% ~ 10% of gross mass.
In lithium ion battery, the effect of binding agent is that electrode active material is attached on collector, and intensifier electrode active material contacts with the electronics between collector with conductive agent, electrode active material.And the negative active core-shell material MnO changing for volume in charge and discharge process 2, adopt the combination of SBR and CMC as binding agent, can also play certain cushioning effect, the structure of stable negative electrode.
The preparation method of above-mentioned electrode slurry and negative electrode can be by MnO 2mix according to the above ratio with conductive agent, then drip respectively successively CMC solution and SBR solution, then add water, stir and form this electrode slurry.The solvent of this CMC solution and SBR solution is water.This electrode slurry is evenly coated on Copper Foil, copper mesh, nickel foil or nickel screen, after oven dry, cuts into negative electrode.
In above-mentioned electrode slurry and negative electrode, this MnO 2can be full particle, hollow ball, nanofiber, nanometer rods and nanotube, but be not limited to full particle, hollow ball, nanofiber, nanometer rods and nanotube.
In one embodiment, this MnO 2for nanotube, this MnO 2the diameter of nanotube is about 50 nanometer～200 nanometers.This MnO 2the pipe thickness of nanotube is about 5 nanometer～30 nanometers.This MnO 2nanotube is linear structure.
This MnO 2the preparation method of nanotube can be:
S1, by potassium permanganate (KMnO 4), hydrogen chloride (HCl) and surfactant polyvinylpyrrolidone (PVP) be mixed to form a mixed liquor in water; And
S2 carries out this mixed liquor hydro-thermal reaction in water heating kettle, and reaction temperature is 120 ℃ ~ 180 ℃, generates MnO 2nanotube.
Particularly, in this step S1, can respectively potassium permanganate and dissolving with hydrochloric acid be configured to solution in deionized water, then this liquor potassic permanganate is mixed with hydrochloric acid solution, then add PVP as surfactant, form the described mixed liquor that contains potassium permanganate, HCl and PVP.In this mixed liquor, the mol ratio of potassium permanganate and HCl can be 1:10 ~ 4:1, PVP add quality optimization be potassium permanganate quality 0.01% ~ 10%, more preferably 0.1% ~ 1%.In this mixed liquor, the concentration of potassium permanganate is preferably 0.01 mol/L ~ 1 mol/L.
In this step S2, this mixed liquor is put into hydrothermal reaction kettle, water heating kettle is sealed and be heated to 120 ℃ ~ 180 ℃ and carry out hydro-thermal reaction, in this reaction temperature temperature retention time, be 1 hour ~ 48 hours.
Water heating kettle naturally cools to room temperature after completion of the reaction, collects the black precipitate in water heating kettle, with deionized water, washs to remove foreign ion, then at air drying, obtains MnO 2nanotube.
The embodiment of the present invention further provides a kind of lithium ion battery, and this lithium ion battery comprises above-mentioned negative electrode, and further comprises positive electrode and the nonaqueous electrolyte between this positive electrode and negative electrode.This positive electrode can comprise plus plate current-collecting body and be attached to the positive electrode material layer of this anode collection surface, and this plus plate current-collecting body can be aluminium or titanium, and this positive electrode material layer comprises positive electrode active materials, conductive agent and binding agent.This positive electrode active materials can be existing anode active material of lithium ion battery, as cobalt acid lithium, lithium nickelate, LiMn2O4 and LiFePO4 etc.This nonaqueous electrolyte can be existing lithium ion battery electrolyte, as nonaqueous electrolytic solution or solid electrolyte film.Adopt the lithium ion battery of this nonaqueous electrolytic solution further to comprise and be arranged on barrier film between this positive electrode material layer and negative electrode material layer.Adopt the lithium ion battery of this solid electrolyte film that this solid electrolyte film is arranged between this positive electrode material layer and negative electrode material layer.This nonaqueous electrolytic solution comprises solvent and is dissolved in the solute of solvent, this solvent can be enumerated as one or more in cyclic carbonate, linear carbonate, ring-type ethers, chain ethers, nitrile and amide-type, as ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton, oxolane, 1,2-dimethoxy-ethane, acetonitrile and dimethyl formamide.This solute can be enumerated as LiPF 6, LiBF 4, LiCF 3sO 3, LiAsF 6, LiClO 4and one or more in LiBOB.The material of this solid electrolyte film can be enumerated as LiI, LiN 3or the mixing of the solute of the polymeric matrix such as polyoxyethylene or polyacrylonitrile and above-mentioned nonaqueous electrolytic solution.
The binder system CMC that the embodiment of the present invention provides and the combination of SBR are aqua type binding agents, adopt water as dispersant.And at present for lithium ion battery anode active material MnO 2the PVDF binding agent adopting is organic solvent type binding agent, need to adopt NMP as dispersant.Owing to adopting cheap water as dispersant, therefore adopt the binding agent of the combination of CMC and SBR to reduce costs significantly, and required use amount also can reduce.The more important thing is the negative active core-shell material MnO changing for volume in charge and discharge process 2, adopt the combination of SBR and CMC as binding agent, can also play certain cushioning effect, the structure of stable negative electrode.Be binder phase ratio with adopting PVDF, the embodiment of the present invention adopts the combination of CMC and SBR as binding agent and MnO 2coordinate the negative plate of making to have better chemical property, specific capacity is higher, stable cycle performance, and the combination that demonstrates CMC and SBR is applied to MnO as binding agent 2the lithium ion battery of negative active core-shell material has good prospect.
Embodiment 1
By MnO 2nanotube, conductive agent acetylene black, SBR and CMC in mass ratio 60:30:5:5 mix, and add water to stir and make slurry, are evenly applied on Copper Foil, cut into circular negative electrode pole piece after oven dry, form lithium ion battery carry out constant current charge-discharge experiment with lithium metal.Electrolyte is for containing 1mol/l LiPF 6eC/DEC (1:1, W/W) solvent.
Refer to Fig. 1, this lithium ion battery is carried out to the test of electrochemistry cycle performance, charging and discharging currents is 100mA/g, and charging/discharging voltage scope is 0.01V-3V.First discharge specific capacity is about 1593mAh/g, and charge ratio capacity is about 1119 mAh/g, and the specific discharge capacity of 100 circulations is about 1100mAh/g, and charge ratio capacity is about 1086mAh/g, and reversible specific capacity is greater than 1000mAh/g.
Embodiment 2
By MnO 2nanotube, conductive agent acetylene black, SBR and CMC in mass ratio 50:30:10:10 mix, and add water to stir and make slurry, are evenly applied on Copper Foil, cut into circular negative electrode pole piece after oven dry, form lithium ion battery carry out constant current charge-discharge experiment with lithium metal.Electrolyte is for containing 1mol/l LiPF 6eC/DEC (1:1, W/W) solvent.
This lithium ion battery is carried out to the test of electrochemistry cycle performance, and charging and discharging currents is 100mA/g, and charging/discharging voltage scope is 0.01V-3V.First discharge specific capacity is about 820mAh/g, and charge ratio capacity is 582 mAh/g.
Embodiment 3
By MnO 2nanotube, conductive agent acetylene black, SBR and CMC in mass ratio 60:25:10:5 mix, and add water to stir and make slurry, are evenly applied on Copper Foil, cut into circular negative electrode pole piece after oven dry, form lithium ion battery carry out constant current charge-discharge experiment with lithium metal.Electrolyte is for containing 1mol/l LiPF 6eC/DEC (1:1, W/W) solvent.
This lithium ion battery is carried out to the test of electrochemistry cycle performance, and charging and discharging currents is 100mA/g, and charging/discharging voltage scope is 0.01V-3V.First discharge specific capacity is about 930mAh/g, and charge ratio capacity is 655 mAh/g.
Embodiment 4
By MnO 2nanotube, conductive agent acetylene black, SBR and CMC in mass ratio 60:25:5:10 mix, and add water to stir and make slurry, are evenly applied on Copper Foil, cut into circular negative electrode pole piece after oven dry, form lithium ion battery carry out constant current charge-discharge experiment with lithium metal.Electrolyte is for containing 1mol/l LiPF 6eC/DEC (1:1, W/W) solvent.
This lithium ion battery is carried out to the test of electrochemistry cycle performance, and charging and discharging currents is 100mA/g, and charging/discharging voltage scope is 0.01V-3V.First discharge specific capacity is about 891mAh/g, and charge ratio capacity is 611 mAh/g.
Embodiment 5:
By MnO 2nanotube, conductive agent acetylene black, SBR and CMC in mass ratio 60:38:1:1 mix, and add water to stir and make slurry, are evenly applied on Copper Foil, cut into circular negative electrode pole piece after oven dry, form lithium ion battery carry out constant current charge-discharge experiment with lithium metal.Electrolyte is for containing 1mol/l LiPF 6eC/DEC (1:1, W/W) solvent.
This lithium ion battery is carried out to the test of electrochemistry cycle performance, and charging and discharging currents is 100mA/g, and charging/discharging voltage scope is 0.01V-3V.First discharge specific capacity is about 210mAh/g, and charge ratio capacity is 151 mAh/g.
Embodiment 6:
By MnO 2nanotube, conductive agent acetylene black, SBR and CMC in mass ratio 50:36:7:7 mix, and add water to stir and make slurry, are evenly applied on Copper Foil, cut into circular negative electrode pole piece after oven dry, form lithium ion battery carry out constant current charge-discharge experiment with lithium metal.Electrolyte is for containing 1mol/l LiPF 6eC/DEC (1:1, W/W) solvent.
This lithium ion battery is carried out to the test of electrochemistry cycle performance, and charging and discharging currents is 100mA/g, and charging/discharging voltage scope is 0.01V-3V.First discharge specific capacity is about 947mAh/g, and charge ratio capacity is 683 mAh/g.
Embodiment 7
By MnO 2particle, conductive agent acetylene black, SBR and CMC in mass ratio 60:30:5:5 mix, and add water to stir and make slurry, are evenly applied on Copper Foil, cut into circular negative electrode pole piece after oven dry, form lithium ion battery carry out constant current charge-discharge experiment with lithium metal.Electrolyte is for containing 1mol/l LiPF 6eC/DEC (1:1, W/W) solvent.
This lithium ion battery is carried out to the test of electrochemistry cycle performance, and charging and discharging currents is 100mA/g, and charging/discharging voltage scope is 0.01V-3V.First discharge specific capacity is about 914mA/g, and charge ratio capacity is about 638mA/g.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention, within all should being included in the present invention's scope required for protection.

Claims (10)

1. an electrode slurry, for making the negative electrode of lithium ion battery, is characterized in that, comprises manganese dioxide, butadiene-styrene rubber, carboxymethyl cellulose, water and conductive agent.
2. electrode slurry as claimed in claim 1, is characterized in that, the mass ratio of this butadiene-styrene rubber and carboxymethyl cellulose is 1:5 to 5:1.
3. electrode slurry as claimed in claim 1, is characterized in that, in this manganese dioxide, conductive agent, butadiene-styrene rubber and carboxymethyl cellulose, the quality of butadiene-styrene rubber accounts for 1% to 10%, and the quality of carboxymethyl cellulose accounts for 1% to 10%.
4. electrode slurry as claimed in claim 1, is characterized in that, this manganese dioxide is manganese dioxide nano pipe.
5. electrode slurry as claimed in claim 1, is characterized in that, manganese dioxide, butadiene-styrene rubber, carboxymethyl cellulose, water and conductive agent, consists of.
6. a negative electrode for lithium ion battery, comprises negative current collector and is attached to the negative electrode material layer of this negative pole currect collecting surface, it is characterized in that, this negative electrode material layer comprises manganese dioxide, butadiene-styrene rubber, carboxymethyl cellulose and conductive agent.
7. the negative electrode of lithium ion battery as claimed in claim 6, is characterized in that, the mass ratio of this butadiene-styrene rubber and carboxymethyl cellulose is 1:5 to 5:1.
8. the negative electrode of lithium ion battery as claimed in claim 6, is characterized in that, the quality of this butadiene-styrene rubber accounts for 1% to 10%, and the quality of carboxymethyl cellulose accounts for 1% to 10%.
9. the negative electrode of lithium ion battery as claimed in claim 1, is characterized in that, this manganese dioxide is manganese dioxide nano pipe.
10. a lithium ion battery, comprises as the negative electrode of the lithium ion battery in any one in claim 6 to 9, and further comprises positive electrode and the nonaqueous electrolyte between this positive electrode and negative electrode.
CN201310560322.7A 2013-11-12 2013-11-12 Electrode slurry, negative electrode and lithium ion battery using negative electrode Pending CN103647040A (en)

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WO2015070706A1 (en) * 2013-11-12 2015-05-21 江苏华东锂电技术研究院有限公司 Electrode slurry, negative electrode, and lithium ion battery using the same
CN108539121A (en) * 2018-04-16 2018-09-14 江西迪芯能源科技有限公司 A kind of lithium ion battery anode slurry and lithium ion battery
CN108987715A (en) * 2018-07-23 2018-12-11 芜湖彰鸿工程技术有限公司 A kind of lithium ion battery anode slurry and preparation method thereof

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CN115594223A (en) * 2022-10-25 2023-01-13 广东邦普循环科技有限公司（Cn） Modified lithium ion sieve, manganese dioxide adsorbent, preparation method and application of manganese dioxide adsorbent, and method for extracting lithium from salt lake

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