CN105304858A - Lithium ion battery, negative plate thereof and preparation method thereof - Google Patents
Lithium ion battery, negative plate thereof and preparation method thereof Download PDFInfo
- Publication number
- CN105304858A CN105304858A CN201410326711.8A CN201410326711A CN105304858A CN 105304858 A CN105304858 A CN 105304858A CN 201410326711 A CN201410326711 A CN 201410326711A CN 105304858 A CN105304858 A CN 105304858A
- Authority
- CN
- China
- Prior art keywords
- active material
- binding agent
- based active
- lithium ion
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium ion battery, a negative plate thereof and a preparation method thereof. The negative plate comprises a negative electrode current collector, and a negative film which is arranged on the negative electrode current collector and comprises a negative electrode active material, a negative electrode adhesive and a conductive agent of the negative electrode. The negative electrode active material comprises a silicon-based active material and a carbon-based active material; the negative electrode adhesive is distributed on the surface of the negative electrode active material; the surface of the silicon-based active material contains -OH; the negative electrode adhesive at least comprises a -COOM adhesive; and the mass ratio of the negative electrode adhesive distributed on the surface of the silicon-based active material to the silicon-based active material is larger than the mass ratio of the negative electrode adhesive distributed on the surface of the carbon-based active material to the carbon-based active material. The negative plate provided by the invention is used for improving the binding power of granules of the silicon-based active material and can solve the problem that the charge and discharge performance of the carbon-based active material is deteriorated due to excessive negative electrode adhesive. The lithium ion battery provided by the invention has good low temperature discharge performance and high temperature cycling performance.
Description
Technical field
The present invention relates to cell art, particularly relate to a kind of lithium ion battery and negative plate thereof and preparation method.
Background technology
There is due to lithium ion battery the features such as energy density is high, the life-span is long, self discharge is low, memory-less effect, be therefore widely used in the portable type electronic products such as mobile phone, notebook computer, digital camera.But the fast development of miniaturized, the intelligent and multifunction of various portable type electronic product, has higher requirement to the energy density of lithium ion battery.
At present, lithium ion battery mainly uses carbon-based active material based on graphite as negative active core-shell material, and the gram volume that carbon-based active material is lower limits the further lifting of the energy density of lithium ion battery.Compared with carbon-based active material, silicon-based active material has very high gram volume, uses silicon-based active material as the negative active core-shell material of lithium ion battery, can significantly improve the energy density of lithium ion battery.But the change in volume of silicon-based active material in charge and discharge process is very large, its particle easily breaks pulverizings under huge stress, causes intergranular contact to be deteriorated, conductivity reduction, and then causes the capacity sharp-decay after lithium ion battery circulation.Silicon-based active material and carbon-based active material, much smaller than silicon-based active material, are mixed and mix negative active core-shell material and effectively can alleviate change in volume in charge and discharge process by the change in volume of carbon-based active material in charge and discharge process.But in the mixing negative active core-shell material of routine, binding agent is evenly distributed on the surface of carbon-based active material and silicon-based active material.Lead lithium ion poor-performing due to binding agent, if the too high levels of binding agent, the charge-discharge performance of carbon-based active material can be had a strong impact on, cause occurring analysing the problem such as lithium, low temperature discharge capacity be low; If the content of binding agent is too low, then cannot bond the more serious silicon-based active material that expands, and cause the negative plate bounce-back in charge and discharge process comparatively large, and then the thickness swelling of lithium ion battery is serious.
Summary of the invention
In view of Problems existing in background technology, the object of the present invention is to provide a kind of lithium ion battery and negative plate thereof and preparation method, described negative plate had both improve the cohesive force between the particle of silicon-based active material, the problem that the charge-discharge performance that can improve again the carbon-based active material that negative pole binding agent too much causes worsens, described lithium ion battery has good low temperature performance and high temperature cyclic performance.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of negative plate of lithium ion battery, it comprises: negative current collector; And cathode membrane, to be arranged on negative current collector and to comprise negative active core-shell material, negative pole binding agent and negative pole conductive agent.Negative active core-shell material comprises silicon-based active material and carbon-based active material; The surface distributed of negative active core-shell material has negative pole binding agent;-OH is contained on the surface of silicon-based active material; Negative pole binding agent at least comprises the binding agent containing-COOM, and wherein, M is selected from the one in H, Li, Na, K, Mg, Al, Ca, Zn; Wherein, the negative pole binding agent of silicon-based active material surface distributed and the mass ratio of silicon-based active material are greater than the negative pole binding agent of carbon-based active material surface distributed and the mass ratio of carbon-based active material.
In a second aspect of the present invention, the invention provides a kind of preparation method of negative plate of lithium ion battery, for the preparation of the negative plate of the lithium ion battery of first aspect present invention, comprise step: (1) is by silicon-based active material, first conductive agent, first binding agent adds in solvent deionized water in proportion and is uniformly mixed, pH value is regulated to be less than 7 afterwards, the also Keep agitation that heats up afterwards makes the solid content of slurry reach setting, obtain the first slurry, wherein,-OH is contained on the surface of silicon-based active material, first binding agent at least comprises the binding agent containing-COOM, wherein, M is selected from H, Li, Na, K, Mg, Al, Ca, one in Zn, (2) carbon-based active material, the second conductive agent, the second binding agent are added in solvent deionized water be in proportion uniformly mixed, obtain the second slurry that solid content is setting, (3) the first slurry and the second slurry are mixed and stir, obtain mixed slurry, wherein, negative active core-shell material comprises silicon-based active material and carbon-based active material, the surface distributed of negative active core-shell material has negative pole binding agent, negative pole binding agent comprises the first binding agent and the second binding agent, negative pole conductive agent comprises the first conductive agent and the second conductive agent, and the negative pole binding agent of silicon-based active material surface distributed and the mass ratio of silicon-based active material are greater than the negative pole binding agent of carbon-based active material surface distributed and the mass ratio of carbon-based active material, (4) mixed slurry is coated on negative current collector, after drying, namely obtains the negative plate of lithium ion battery.
In a third aspect of the present invention, the invention provides a kind of lithium ion battery, it comprises: positive plate; Negative plate; Barrier film, is interval between positive plate and negative plate; And electrolyte.Described negative plate is the negative plate of lithium ion battery according to a first aspect of the present invention.
Beneficial effect of the present invention is as follows:
The preparation method of the negative plate of lithium ion battery of the present invention can realize the uneven distribution of negative pole binding agent on silicon-based active material and carbon-based active material surface, and the mass ratio of the negative pole binding agent of silicon-based active material surface distributed and silicon-based active material is greater than the negative pole binding agent of carbon-based active material surface distributed and the mass ratio of carbon-based active material, thus the cohesive force between the particle that can improve silicon-based active material, the bounce-back of the cathode membrane suppressing the expansion of the particle of silicon-based active material to cause, carbon-based active material can also be made to have good chemical property simultaneously, and then make lithium ion battery have good low temperature performance and high temperature cyclic performance.
Embodiment
The following detailed description of lithium ion battery according to the present invention and negative plate thereof and preparation method and embodiment, comparative example and test result.
First the negative plate of lithium ion battery is according to a first aspect of the present invention described.
The negative plate of lithium ion battery according to a first aspect of the present invention, comprising: negative current collector; And cathode membrane, to be arranged on negative current collector and to comprise negative active core-shell material, negative pole binding agent and negative pole conductive agent.Negative active core-shell material comprises silicon-based active material and carbon-based active material; The surface distributed of negative active core-shell material has negative pole binding agent;-OH is contained on the surface of silicon-based active material; Negative pole binding agent at least comprises the binding agent containing-COOM, and wherein, M is selected from the one in H, Li, Na, K, Mg, Al, Ca, Zn; Wherein, the negative pole binding agent of silicon-based active material surface distributed and the mass ratio of silicon-based active material are greater than the negative pole binding agent of carbon-based active material surface distributed and the mass ratio of carbon-based active material.
In the negative plate of lithium ion battery described according to a first aspect of the present invention, described negative current collector can be Copper Foil.
In the negative plate of lithium ion battery described according to a first aspect of the present invention, described silicon-based active material can be selected from silicon, SiO
x(0.6<x<1.5) one or more, in silicon/carbon complex.Wherein, the carbon in described silicon/carbon complex can be selected from one or more in Delanium, native graphite, soft carbon, hard carbon, carbon fiber, carbonaceous mesophase spherules, carbon nano-tube (CNT), Graphene.
In the negative plate of lithium ion battery described according to a first aspect of the present invention, described carbon-based active material can be selected from one or more in Delanium, native graphite, hard carbon, soft carbon, carbon fiber, carbonaceous mesophase spherules, carbon nano-tube (CNT), Graphene.
In the negative plate of lithium ion battery described according to a first aspect of the present invention, described negative pole binding agent also can comprise one or more in butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
In the negative plate of lithium ion battery described according to a first aspect of the present invention, the described binding agent containing-COOM can be selected from sodium carboxymethylcellulose (CMC), polyacrylic acid (PAA), polyacrylate (PAAM, wherein, M is selected from the one in Li, Na, K, Mg, Al, Ca, Zn), one or more in sodium alginate (ALG).
Secondly the preparation method of the negative plate of lithium ion battery is according to a second aspect of the present invention described.
The preparation method of the negative plate of lithium ion battery according to a second aspect of the present invention, for the preparation of the negative plate of the lithium ion battery of first aspect present invention, comprise step: (1) is by silicon-based active material, first conductive agent, first binding agent adds in solvent deionized water in proportion and is uniformly mixed, pH value is regulated to be less than 7 afterwards, the also Keep agitation that heats up afterwards makes the solid content of slurry reach setting, obtain the first slurry, wherein,-OH is contained on the surface of silicon-based active material, first binding agent at least comprises the binding agent containing-COOM, wherein, M is selected from H, Li, Na, K, Mg, Al, Ca, one in Zn, (2) carbon-based active material, the second conductive agent, the second binding agent are added in solvent deionized water be in proportion uniformly mixed, obtain the second slurry that solid content is setting, (3) the first slurry and the second slurry are mixed and stir, obtain mixed slurry, wherein, negative active core-shell material comprises silicon-based active material and carbon-based active material, the surface distributed of negative active core-shell material has negative pole binding agent, negative pole binding agent comprises the first binding agent and the second binding agent, negative pole conductive agent comprises the first conductive agent and the second conductive agent, and the negative pole binding agent of silicon-based active material surface distributed and the mass ratio of silicon-based active material are greater than the negative pole binding agent of carbon-based active material surface distributed and the mass ratio of carbon-based active material, (4) mixed slurry is coated on negative current collector, after drying, namely obtains the negative plate of lithium ion battery.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, first slurry comprises the binding agent containing-COOM, the binding agent of-COOM should be contained under sour environment, stir by heating up, can esterification be there is with-the OH of the particle surface of silicon-based active material and produce chemical bond, its effect is stronger than physisorption, thus the binding agent containing-COOM can be made firmly to be bonded in the particle surface of silicon-based active material.When the first slurry mixes with the second slurry, chemical bond is there is between particle due to silicon-based active material and the binding agent containing-COOM, therefore the binding agent containing-COOM can not split away off from the particle surface of silicon-based active material, thus the uneven distribution of negative pole binding agent on the particle of silicon-based active material and the particle of carbon-based active material can be realized, cohesive force between the particle that so both can improve silicon-based active material, the bounce-back of the cathode membrane suppressing the expansion of the particle of silicon-based active material to cause, carbon-based active material can also be made to have good chemical property simultaneously, final lithium ion battery has good low temperature performance and high temperature cyclic performance simultaneously.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1), in the first binding agent, can be (1:99) ~ (10:90) containing the binding agent of-COOM and the mass ratio of silicon-based active material.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1), the first binding agent also can comprise one or more in butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1), described first conductive agent can be selected from one or more in Super-P, conductive black, electrically conductive graphite.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1), oxalic acid, acetic acid or citric acid can be used to regulate pH value.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1), described pH value preferably can be 2 ~ 3.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1), the temperature of described intensification can be 50 DEG C ~ 70 DEG C.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (1), the setting of the solid content of described first slurry can be greater than 65%, preferably can be 70% ~ 80%.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (2), the second binding agent can comprise one or more in binding agent containing-COOM, butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (2), in the second binding agent, can be (0:100) ~ (5:95) containing the binding agent of-COOM and the mass ratio of carbon-based active material.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (2), described second conductive agent can be selected from one or more in Super-P, conductive black, electrically conductive graphite.
In the preparation method of the negative plate of lithium ion battery described according to a second aspect of the present invention, in step (2), the setting of the solid content of described second slurry can be 30% ~ 60%.
Lithium ion battery is according to a third aspect of the present invention described again.
Lithium ion battery according to a third aspect of the present invention, comprising: positive plate; Negative plate; Barrier film, is interval between positive plate and negative plate; And electrolyte.Wherein, described negative plate is the negative plate of lithium ion battery according to a first aspect of the present invention.
Following explanation is according to the embodiment of lithium ion battery of the present invention and negative plate and preparation method and comparative example.
Embodiment 1
1. the preparation of the negative plate of lithium ion battery
(1) to be silicon grain, the first conductive agent SuperP, the first binding agent molecular weight of 3 μm by silicon-based active material D50 be 400000 polyacrylic acid in mass ratio 96:1:3 add in solvent deionized water, fully be uniformly mixed, the pH value of slurry is regulated to be 3 with oxalic acid afterwards, then slurry is slowly warmed up to 60 DEG C and the solid content continuing stirring until slurry is 70%, obtain the first slurry, wherein ,-OH is contained on the surface of silicon grain;
(2) to be Delanium, the second conductive agent SuperP, the second binding agent molecular weight of 15 μm by carbon-based active material D50 be 400000 polyacrylic acid in mass ratio 98:1:1 add in solvent deionized water, fully be uniformly mixed, form the second slurry that solid content is 48%;
(3) the second slurry is slowly joined in the first slurry and be also fully uniformly mixed, obtain mixed slurry, wherein, in mixed slurry, the mass ratio of carbon-based active material and silicon-based active material is 90:10, wherein, negative active core-shell material comprises silicon-based active material and carbon-based active material, the surface distributed of negative active core-shell material has negative pole binding agent, and negative pole binding agent comprises the first binding agent and the second binding agent, and negative pole conductive agent comprises the first conductive agent and the second conductive agent;
(4) mixed slurry is evenly coated on 8 μm of thick negative current collector Copper Foils, after drying, compacting, cut-parts, itemize, soldering polar ear, obtains the negative plate of lithium ion battery.
2. the preparation of the positive plate of lithium ion battery
By positive electrode active materials D50 be 18 μm cobalt acid lithium, positive pole conductive agent SuperP, positive pole binding agent PVDF in mass ratio 96:2:2 add in solvent NMP, anode sizing agent is obtained after being fully uniformly mixed, afterwards anode sizing agent is evenly coated on 14 μm of thick plus plate current-collecting body aluminium foils, after drying, compacting, cut-parts, itemize, soldering polar ear, obtain the positive plate of lithium ion battery.
3. the preparation of the electrolyte of lithium ion battery
The electrolyte of lithium ion battery take concentration as the lithium hexafluoro phosphate (LiPF6) of 1M is lithium salts, with the mixture of ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) for non-aqueous organic solvent, wherein the volume ratio of each carbonic ester is EC:DEC:EMC=1:1:1.
4. the preparation of lithium ion battery
By the positive plate of the lithium ion battery of preparation, negative plate and barrier film (polyethylene, PE) be prepared into that thickness is 4.5mm, width is 42mm, length is the battery core of 61mm through winding and packaging technology, vacuum bakeout 10h at 75 DEG C afterwards, inject electrolyte and leave standstill 24h, obtaining lithium ion battery.
Embodiment 2
Method according to embodiment 1 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
(1) silicon-based active material to be D50 the be SiO1.1 of 3 μm ,-OH is contained on the surface of SiO1.1, the first binding agent to be molecular weight be 800000 Lithium polyacrylate;
(2) carbon-based active material is carbon nano-tube, the second binding agent to be molecular weight be 800000 Lithium polyacrylate.
Embodiment 3
Method according to embodiment 1 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
(1) silicon-based active material to be D50 the be silicon/Delanium compound of 3 μm, wherein,-OH is contained on the surface of silicon/Delanium compound, silicon be coated on Delanium surface and the mass fraction of silicon is the 20%, first binding agent to be molecular weight be 600000 sodium alginate (ALG);
(2) carbon-based active material to be D50 the be hard carbon of 15 μm, the second binding agent to be molecular weight be 600000 sodium alginate (ALG).
Embodiment 4
Method according to embodiment 1 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
(2) by carbon-based active material D50 be 15 μm Delanium, the second conductive agent SuperP, the second binding agent polyvinyl alcohol in mass ratio 98:1:1 add in solvent deionized water, be fully uniformly mixed, formed solid content be 48% the second slurry.
Embodiment 5
Method according to embodiment 1 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
(2) by carbon-based active material D50 be 15 μm Delanium, the second conductive agent SuperP, the second binding agent sodium carboxymethylcellulose and butadiene-styrene rubber in mass ratio 97:1:1:1 add in solvent deionized water, fully be uniformly mixed, form the second slurry that solid content is 48%.
Embodiment 6
Method according to embodiment 5 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
(1) to be silicon grain, the first conductive agent SuperP, the first binding agent molecular weight of 3 μm by silicon-based active material D50 be 800000 Lithium polyacrylate and polyvinyl alcohol in mass ratio 95:1:3:1 add in solvent deionized water, fully be uniformly mixed, the pH value of slurry is regulated to be 3 with oxalic acid afterwards, then slurry is slowly warmed up to 60 DEG C and the solid content continuing stirring until slurry is 70%, obtains the first slurry.
Embodiment 7
Method according to embodiment 6 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
(1) first binding agent is sodium carboxymethylcellulose and butadiene-styrene rubber, and the mass ratio of silicon grain, SuperP, sodium carboxymethylcellulose, butadiene-styrene rubber is 95:1:3:1.
Embodiment 8
Method according to embodiment 7 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
(1) mass ratio of silicon grain, SuperP, sodium carboxymethylcellulose, butadiene-styrene rubber is 93:1:5:1.
Embodiment 9
Method according to embodiment 7 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
(1) mass ratio of silicon grain, SuperP, sodium carboxymethylcellulose, butadiene-styrene rubber is 91:1:7:1.
Embodiment 10
Method according to embodiment 7 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
The pH value of (1) first slurry is 2.
Embodiment 11
Method according to embodiment 7 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
The pH value of (1) first slurry is 5.
Embodiment 12
Method according to embodiment 7 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
The warming temperature of (1) first slurry is 50 DEG C and the solid content continuing stirring until the first slurry is 65%.
Embodiment 13
Method according to embodiment 7 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
The warming temperature of (1) first slurry is 70 DEG C and the solid content continuing stirring until the first slurry is 80%.
Comparative example 1
Method according to embodiment 1 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
The mixture (mass ratio is 90:10) of to be the Delanium of 15 μm and D50 by negative active core-shell material D50 the be silicon grain of 3 μm, negative pole conductive agent SuperP, negative pole binding agent sodium carboxymethylcellulose and butadiene-styrene rubber in mass ratio 97:1:1:1 add in solvent deionized water, fully be uniformly mixed, forming solid content is the slurry of 48%, afterwards slurry being evenly coated in thickness is on the negative current collector Copper Foil of 8 μm, after super-dry, compacting, cut-parts, itemize, soldering polar ear, obtain the negative plate of lithium ion battery.
Comparative example 2
Method according to comparative example 1 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
The mass ratio of negative active core-shell material, SuperP, sodium carboxymethylcellulose and butadiene-styrene rubber is 95:1:3:1.
Comparative example 3
Method according to embodiment 7 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
(1) pH value of the first slurry is not regulated.
Comparative example 4
Method according to embodiment 7 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
(1), after regulating pH value, warming temperature is not carried out, but in ambient operation.
Comparative example 5
Method according to embodiment 7 prepares lithium ion battery, except following difference:
1. the preparation of the negative plate of lithium ion battery
The solid content of (1) first slurry is 55%.
Finally provide the lithium ion battery of embodiment 1-13 and comparative example 1-5 and the performance test process of negative plate and preparation method thereof and test result.
(1) the cohesive force test of cathode membrane
Cathode membrane after colding pressing is prepared into length is 20cm, width is the sample of 15mm, drawing high the cohesive force of test airborne measurements cathode membrane, wherein draw speed is 100mm/s.
(2) the bounce-back ratio test of negative plate
The thickness of the negative plate after colding pressing with miking, is designated as T
1; Afterwards by lithium ion battery at 25 DEG C with 0.7C multiplying power constant current charge to 3.85V, take lithium ion battery apart afterwards, and be again designated as T with the thickness of miking negative plate
2.
Bounce-back ratio (%)=(T of negative plate
2-T
1)/T
1× 100%.
(3) the low temperature performance test of lithium ion battery
At 25 DEG C, by lithium ion battery with 0.7C multiplying power constant current charge to 4.20V, afterwards with 4.20V constant voltage charge to 0.05C, then with 0.5C multiplying power constant-current discharge to 3.0V, the discharge capacity at recording 25 DEG C; Again by lithium ion battery with 0.7C multiplying power constant current charge to 4.20V, afterwards with 4.20V constant voltage charge to 0.05C, then at-10 DEG C with 0.5C multiplying power constant-current discharge to 3.0V, the discharge capacity at record-10 DEG C.
Discharge capacity × 100% at discharge capacity/25 at the low temperature discharge ratio (%) of lithium ion battery=-10 DEG C DEG C.
(4) the high temperature circulation expansion rate test of lithium ion battery
At 45 DEG C, by lithium ion battery with 0.7C multiplying power constant current charge to 4.20V, afterwards with 4.20V constant voltage charge to 0.05C, measure the thickness of the lithium ion battery of fully charged state, be designated as original depth, then with 0.5C multiplying power constant-current discharge to 3.0V, this is a charge and discharge cycles process; Repeat above charge and discharge cycles process 300 times, and measure the thickness of the lithium ion battery of the 300th circulation time fully charged state, be designated as the thickness after circulation.
High temperature circulation expansion rate (%)=(thickness/original depth-1 after circulation) × 100% of lithium ion battery.
Table 1 provides parameter and the performance test results of embodiment 1-13 and comparative example 1-5.
Next the performance test results of embodiment 1-13 and comparative example 1-5 is analyzed.
As can be seen from the contrast of embodiment 1-13 and comparative example 1-2, the negative plate of the comparative example 1-2 distributed at carbon-based active material and silicon-based active material surface uniform with negative pole binding agent is compared, negative pole binding agent of the present invention has higher cathode membrane cohesive force and lower thickness bounce-back ratio at the negative plate of carbon-based active material and silicon-based active material surface uneven distribution, and then lithium ion battery has good low temperature performance and high temperature cyclic performance.This is in the negative plate owing to obtaining in preparation method of the present invention, negative pole binding agent uneven distribution on negative active core-shell material, and the mass ratio of the negative pole binding agent of silicon-based active material surface distributed and silicon-based active material is greater than the negative pole binding agent of carbon-based active material surface distributed and the mass ratio of carbon-based active material, cohesive force between the particle that can improve silicon-based active material so well, the bounce-back of the cathode membrane suppressing the expansion of the particle of silicon-based active material to cause, the problem of the low temperature discharge capacity step-down of the too high lithium ion battery caused of the negative pole binder content on carbon-based active material surface can be avoided again simultaneously, thus make carbon-based active material have good chemical property, and then lithium ion battery has good low temperature performance and high temperature cyclic performance.
When the binding agent containing-COOM added when preparing slurry is 1% (comparative example 1), due to the binding agent very few (namely the negative pole binding agent on silicon-based active material surface is very few) containing-COOM on silicon-based active material surface, cause the cohesive force of cathode membrane too low, be not enough to the expansion suppressing silicon-based active material, and then the thickness bounce-back large percentage of negative plate, the thickness swelling after high-temperature lithium ion battery circulation is serious.When the binding agent containing-COOM added when preparing slurry is 3% (comparative example 2), although the cohesive force of cathode membrane increases, the thickness bounce-back ratio of negative plate reduces, thickness swelling after high-temperature lithium ion battery circulation reduces, but lithium ion battery low temperature discharge ratio significantly reduces.This is the poor-performing due to negative pole binding agent Electolyte-absorptive and transmission lithium ion, and the binding agent (i.e. the too high levels of the negative pole binding agent on carbon-based active material surface) containing-COOM that carbon-based active material surface is too high, add the interface impedance of negative pole, thus cause the low temperature performance of lithium ion battery to be deteriorated.
As can be seen from the contrast of embodiment 7-9, along with the mass percentage of the binding agent containing-COOM on silicon-based active material surface increases (namely the mass percentage of the negative pole binding agent on silicon-based active material surface increases), the cohesive force of cathode membrane increases, the thickness bounce-back ratio of negative plate reduces, lithium ion battery thickness swelling at high temperature reduces, but the low temperature performance of lithium ion battery is deteriorated.This is because too much negative pole binding agent can have a negative impact to the dynamic performance of silicon-based active material, the simultaneously too much binding agent containing-COOM can not be pinned at silicon-based active material surface completely, in mixed slurry preparation process, the too much binding agent containing-COOM can transfer to carbon-based active material surface, thus affects the low temperature performance of carbon-based active material.
As can be seen from the contrast of embodiment 7 and embodiment 10-11, along with the increase of the pH value of the first slurry, the cohesive force of cathode membrane reduces gradually, the thickness bounce-back ratio of negative plate increases, the low temperature discharge ratio of lithium ion battery first increases rear reduction, lithium ion battery thickness swelling at high temperature increases gradually, and therefore the pH value of the first slurry should be moderate.It can also be seen that from the contrast of embodiment 7 and comparative example 3, owing to regulating the pH value of the first slurry in comparative example 3, therefore the performance of negative plate and lithium ion battery is all poor.
As can be seen from the contrast of embodiment 7 and embodiment 12-13, along with the warming temperature of the first slurry and the increase of solid content, the cohesive force of cathode membrane increases gradually, the thickness bounce-back ratio of negative plate first reduces rear increase, the low temperature discharge ratio of lithium ion battery first increases rear reduction, lithium ion battery thickness swelling at high temperature takes the lead in reducing rear increase, and therefore the warming temperature of the first slurry and solid content should be moderate.It can also be seen that from the contrast of embodiment 7 and comparative example 4, when the first slurry at room temperature stirs, the performance of negative plate and lithium ion battery is all poor.It can also be seen that from the contrast of embodiment 7 and comparative example 5, when the solid content of the first slurry is too low, the performance of negative plate and lithium ion battery is also all poor.This cannot carry out sufficient esterification with containing the binding agent of-COOM due to silicon-based active material surface-OH, the binding agent containing-COOM is caused only to there is the surface of silicon-based active material with the form of physical absorption, when the first slurry is mixed with the second slurry, binding agent containing-COOM can be redistributed on silicon-based active material surface, finally cause the distribution trend of negative pole binding agent on the surface of silicon-based active material and carbon-based active material evenly, therefore the cohesive force of cathode membrane reduces, thickness bounce-back ratio and the lithium ion battery thickness swelling at high temperature of negative plate increase, and the low temperature performance of lithium ion battery is deteriorated.
Claims (10)
1. a negative plate for lithium ion battery, comprising:
Negative current collector; And
Cathode membrane, to be arranged on negative current collector and to comprise negative active core-shell material, negative pole binding agent and negative pole conductive agent;
It is characterized in that,
Negative active core-shell material comprises silicon-based active material and carbon-based active material;
The surface distributed of negative active core-shell material has negative pole binding agent;
-OH is contained on the surface of silicon-based active material;
Negative pole binding agent at least comprises the binding agent containing-COOM, and wherein, M is selected from the one in H, Li, Na, K, Mg, Al, Ca, Zn;
Wherein, the negative pole binding agent of silicon-based active material surface distributed and the mass ratio of silicon-based active material are greater than the negative pole binding agent of carbon-based active material surface distributed and the mass ratio of carbon-based active material.
2. the negative plate of lithium ion battery according to claim 1, is characterized in that,
Silicon-based active material is selected from silicon, SiO
x(0.6<x<1.5) one or more, in silicon/carbon complex, wherein, the carbon in silicon/carbon complex is selected from one or more in Delanium, native graphite, soft carbon, hard carbon, carbon fiber, carbonaceous mesophase spherules, carbon nano-tube (CNT), Graphene;
Carbon-based active material is selected from one or more in Delanium, native graphite, soft carbon, hard carbon, carbon fiber, carbonaceous mesophase spherules, carbon nano-tube (CNT), Graphene.
3. the negative plate of lithium ion battery according to claim 1, is characterized in that, negative pole binding agent also comprises one or more in butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
4. the negative plate of lithium ion battery according to claim 1, it is characterized in that, the described binding agent containing-COOM is selected from sodium carboxymethylcellulose (CMC), polyacrylic acid (PAA), polyacrylate (PAAM, wherein, M is selected from the one in Li, Na, K, Mg, Al, Ca, Zn), one or more in sodium alginate (ALG).
5. a preparation method for the negative plate of lithium ion battery, for the preparation of the negative plate of the lithium ion battery according to any one of claim 1-4, comprises step:
(1) silicon-based active material, the first conductive agent, the first binding agent are added in solvent deionized water be in proportion uniformly mixed, pH value is regulated to be less than 7 afterwards, the also Keep agitation that heats up afterwards makes the solid content of slurry reach setting, obtain the first slurry, wherein ,-OH is contained on the surface of silicon-based active material, and the first binding agent at least comprises the binding agent containing-COOM, wherein, M is selected from the one in H, Li, Na, K, Mg, Al, Ca, Zn;
(2) carbon-based active material, the second conductive agent, the second binding agent are added in solvent deionized water be in proportion uniformly mixed, obtain the second slurry that solid content is setting;
(3) the first slurry and the second slurry are mixed and stir, obtain mixed slurry, wherein, negative active core-shell material comprises silicon-based active material and carbon-based active material, the surface distributed of negative active core-shell material has negative pole binding agent, negative pole binding agent comprises the first binding agent and the second binding agent, negative pole conductive agent comprises the first conductive agent and the second conductive agent, and the negative pole binding agent of silicon-based active material surface distributed and the mass ratio of silicon-based active material are greater than the negative pole binding agent of carbon-based active material surface distributed and the mass ratio of carbon-based active material;
(4) mixed slurry is coated on negative current collector, after drying, namely obtains the negative plate of lithium ion battery.
6. the preparation method of the negative plate of lithium ion battery according to claim 5, it is characterized in that, in step (1), in the first binding agent is (1:99) ~ (10:90) containing the binding agent of-COOM and the mass ratio of silicon-based active material.
7. the preparation method of the negative plate of lithium ion battery according to claim 5, is characterized in that, in step (1), the first binding agent also comprises one or more in butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
8. the preparation method of the negative plate of lithium ion battery according to claim 5, is characterized in that, in step (2), the second binding agent comprises containing one or more in the binding agent of-COOM, butadiene-styrene rubber, polyvinyl alcohol, POLYPROPYLENE GLYCOL.
9. the preparation method of the negative plate of lithium ion battery according to claim 8, it is characterized in that, in step (2), in the second binding agent is (0:100) ~ (5:95) containing the binding agent of-COOM and the mass ratio of carbon-based active material.
10. a lithium ion battery, comprising:
Positive plate;
Negative plate;
Barrier film, is interval between positive plate and negative plate; And
Electrolyte;
It is characterized in that,
Described negative plate is the negative plate of the lithium ion battery according to any one of claim 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410326711.8A CN105304858B (en) | 2014-07-10 | 2014-07-10 | Lithium ion battery and its negative plate and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410326711.8A CN105304858B (en) | 2014-07-10 | 2014-07-10 | Lithium ion battery and its negative plate and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105304858A true CN105304858A (en) | 2016-02-03 |
| CN105304858B CN105304858B (en) | 2017-12-12 |
Family
ID=55201839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410326711.8A Active CN105304858B (en) | 2014-07-10 | 2014-07-10 | Lithium ion battery and its negative plate and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105304858B (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106571469A (en) * | 2016-12-08 | 2017-04-19 | 长兴天晟能源科技有限公司 | Anode slurry binding agent used for lithium ion batteries |
| CN107863497A (en) * | 2017-09-11 | 2018-03-30 | 深圳市比克动力电池有限公司 | Lithium ion battery silicon cathode material and its preparation method and application |
| WO2018082601A1 (en) | 2016-11-07 | 2018-05-11 | Grst International Limited | Method of preparing battery anode slurries |
| CN108053008A (en) * | 2017-11-29 | 2018-05-18 | 横店集团东磁股份有限公司 | A kind of high frequency RFID electronic label antifreeze plate and preparation method thereof |
| KR20180113375A (en) * | 2017-04-06 | 2018-10-16 | 주식회사 엘지화학 | Anode for secondary battery and method for manufacturing the same |
| KR20180113376A (en) * | 2017-04-06 | 2018-10-16 | 주식회사 엘지화학 | Anode for secondary battery and method for manufacturing the same |
| CN108695508A (en) * | 2018-07-06 | 2018-10-23 | 辽宁九夷锂能股份有限公司 | High-energy lithium battery negative electrode slurry and preparation method thereof |
| CN108780881A (en) * | 2016-03-14 | 2018-11-09 | 株式会社村田制作所 | Secondary battery cathode, secondary cell, battery pack, electric vehicle, accumulating system, electric tool and electronic equipment |
| CN108807955A (en) * | 2018-08-29 | 2018-11-13 | 西安交通大学苏州研究院 | A kind of SiNPs@CA@GO composite material and preparation methods and application |
| CN109638250A (en) * | 2018-12-11 | 2019-04-16 | 佛山市实达科技有限公司 | A kind of anode plate for lithium ionic cell of quickly-chargeable |
| KR20190078882A (en) * | 2017-12-27 | 2019-07-05 | 주식회사 엘지화학 | Binder for lithium-sulfur battery, positive electrode and lithium-sulfur battery comprising the same |
| CN110323445A (en) * | 2019-06-25 | 2019-10-11 | 西安交通大学苏州研究院 | PAA-CA complex phase binder and preparation method thereof |
| WO2020186799A1 (en) * | 2019-03-20 | 2020-09-24 | Ningde Amperex Technology Limited | Anode active material and preparation method thereof, and device using the anode active material |
| CN112038570A (en) * | 2020-09-22 | 2020-12-04 | 合肥国轩高科动力能源有限公司 | Silicon-carbon cathode slurry, slurry mixing method and application |
| CN112736247A (en) * | 2019-10-28 | 2021-04-30 | 广州汽车集团股份有限公司 | Water-based composite binder, negative electrode slurry and preparation method thereof, negative electrode sheet, lithium ion battery cell, lithium ion battery pack and application thereof |
| CN113394363A (en) * | 2020-03-13 | 2021-09-14 | 宁德新能源科技有限公司 | Preparation method of negative pole piece, battery and electronic device |
| US11127945B2 (en) | 2016-06-14 | 2021-09-21 | Nexeon Limited | Electrodes for metal-ion batteries |
| CN113764625A (en) * | 2021-08-26 | 2021-12-07 | 蜂巢能源科技有限公司 | Sulfide silicon-based negative plate, preparation method thereof and all-solid-state lithium ion battery |
| CN113839009A (en) * | 2021-08-23 | 2021-12-24 | 惠州锂威新能源科技有限公司 | Negative electrode slurry and preparation method thereof, negative electrode plate and secondary battery |
| CN113889623A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Silicon negative electrode material, preparation method thereof and lithium ion battery |
| CN114335521A (en) * | 2021-11-22 | 2022-04-12 | 惠州市豪鹏科技有限公司 | Negative plate material, negative plate, battery preparation method and battery |
| CN117293314A (en) * | 2023-09-25 | 2023-12-26 | 浙江煌能新能源科技有限公司 | Adhesive for improving electrical property of silicon-based negative electrode, battery negative electrode and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101350404A (en) * | 2008-09-04 | 2009-01-21 | 上海交通大学 | Lithium ion battery cathode and preparation method thereof |
| CN101969114A (en) * | 2010-09-26 | 2011-02-09 | 东莞新能源科技有限公司 | Lithium-ion secondary battery and preparation method for pole piece thereof |
| US20110165464A1 (en) * | 2010-01-05 | 2011-07-07 | Samsung Sdi Co., Ltd. | Negative Electrode for Rechargeable Lithium Battery and Rechargeable Lithium Battery Including Same |
| CN103887507A (en) * | 2012-12-19 | 2014-06-25 | 三星Sdi株式会社 | Negative electrode for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same |
-
2014
- 2014-07-10 CN CN201410326711.8A patent/CN105304858B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101350404A (en) * | 2008-09-04 | 2009-01-21 | 上海交通大学 | Lithium ion battery cathode and preparation method thereof |
| US20110165464A1 (en) * | 2010-01-05 | 2011-07-07 | Samsung Sdi Co., Ltd. | Negative Electrode for Rechargeable Lithium Battery and Rechargeable Lithium Battery Including Same |
| CN101969114A (en) * | 2010-09-26 | 2011-02-09 | 东莞新能源科技有限公司 | Lithium-ion secondary battery and preparation method for pole piece thereof |
| CN103887507A (en) * | 2012-12-19 | 2014-06-25 | 三星Sdi株式会社 | Negative electrode for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same |
Cited By (49)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108780881B (en) * | 2016-03-14 | 2021-10-26 | 株式会社村田制作所 | Negative electrode for secondary battery, battery pack, electric vehicle, power storage system, electric power tool, and electronic device |
| CN108780881A (en) * | 2016-03-14 | 2018-11-09 | 株式会社村田制作所 | Secondary battery cathode, secondary cell, battery pack, electric vehicle, accumulating system, electric tool and electronic equipment |
| US10868327B2 (en) | 2016-03-14 | 2020-12-15 | Murata Manufacturing Co., Ltd. | Negative electrode for secondary battery, secondary battery, battery pack, electric vehicle, power storage system, power tool, and electronic device |
| EP3469644B1 (en) * | 2016-06-14 | 2022-11-09 | Nexeon Limited | Electrodes for metal-ion batteries |
| US11127945B2 (en) | 2016-06-14 | 2021-09-21 | Nexeon Limited | Electrodes for metal-ion batteries |
| CN109923705B (en) * | 2016-11-07 | 2022-04-05 | 皓智环球有限公司 | Method for preparing battery anode slurry |
| WO2018082601A1 (en) | 2016-11-07 | 2018-05-11 | Grst International Limited | Method of preparing battery anode slurries |
| KR102272893B1 (en) | 2016-11-07 | 2021-07-05 | 쥐알에스티 인터내셔널 리미티드 | Method for preparing anode slurry for batteries |
| EP3535794A4 (en) * | 2016-11-07 | 2020-07-15 | GRST International Limited | Method of preparing battery anode slurries |
| US11502288B2 (en) | 2016-11-07 | 2022-11-15 | Grst International Limited | Method of preparing battery anode slurries |
| CN109923705A (en) * | 2016-11-07 | 2019-06-21 | 皓智环球有限公司 | The method for preparing galvanic anode slurry |
| KR20190077399A (en) * | 2016-11-07 | 2019-07-03 | 쥐알에스티 인터내셔널 리미티드 | Method for producing battery anode slurry |
| JP2019537212A (en) * | 2016-11-07 | 2019-12-19 | ジーアールエスティー・インターナショナル・リミテッド | Battery anode slurry preparation method |
| CN106571469A (en) * | 2016-12-08 | 2017-04-19 | 长兴天晟能源科技有限公司 | Anode slurry binding agent used for lithium ion batteries |
| CN110506350A (en) * | 2017-04-06 | 2019-11-26 | 株式会社Lg化学 | Secondary battery cathode and its manufacturing method |
| CN110521031A (en) * | 2017-04-06 | 2019-11-29 | 株式会社Lg化学 | Secondary battery cathode and its manufacturing method |
| KR102248864B1 (en) * | 2017-04-06 | 2021-05-06 | 주식회사 엘지화학 | Anode for secondary battery and method for manufacturing the same |
| US11495785B2 (en) | 2017-04-06 | 2022-11-08 | Lg Energy Solution, Ltd. | Negative electrode for secondary battery and method for producing same |
| CN110506350B (en) * | 2017-04-06 | 2023-02-21 | 株式会社Lg新能源 | Negative electrode for secondary battery and method for producing same |
| US11735713B2 (en) | 2017-04-06 | 2023-08-22 | Lg Energy Solution, Ltd. | Negative electrode for secondary battery, and method for producing same |
| KR20180113376A (en) * | 2017-04-06 | 2018-10-16 | 주식회사 엘지화학 | Anode for secondary battery and method for manufacturing the same |
| KR20180113375A (en) * | 2017-04-06 | 2018-10-16 | 주식회사 엘지화학 | Anode for secondary battery and method for manufacturing the same |
| KR102248865B1 (en) * | 2017-04-06 | 2021-05-06 | 주식회사 엘지화학 | Anode for secondary battery and method for manufacturing the same |
| CN107863497A (en) * | 2017-09-11 | 2018-03-30 | 深圳市比克动力电池有限公司 | Lithium ion battery silicon cathode material and its preparation method and application |
| CN108053008A (en) * | 2017-11-29 | 2018-05-18 | 横店集团东磁股份有限公司 | A kind of high frequency RFID electronic label antifreeze plate and preparation method thereof |
| KR20190078882A (en) * | 2017-12-27 | 2019-07-05 | 주식회사 엘지화학 | Binder for lithium-sulfur battery, positive electrode and lithium-sulfur battery comprising the same |
| CN111386621A (en) * | 2017-12-27 | 2020-07-07 | 株式会社Lg化学 | Binder for lithium-sulfur battery, positive electrode comprising same, and lithium-sulfur battery |
| CN111386621B (en) * | 2017-12-27 | 2023-05-02 | 株式会社Lg新能源 | Binder for lithium-sulfur battery, positive electrode comprising same, and lithium-sulfur battery |
| EP3664200A4 (en) * | 2017-12-27 | 2020-11-25 | Lg Chem, Ltd. | Binder for lithium-sulfur battery, positive electrode comprising same, and lithium-sulfur battery |
| US11038177B2 (en) | 2017-12-27 | 2021-06-15 | Lg Chem, Ltd. | Binder for lithium-sulfur battery, positive electrode comprising same, and lithium-sulfur battery |
| CN108695508A (en) * | 2018-07-06 | 2018-10-23 | 辽宁九夷锂能股份有限公司 | High-energy lithium battery negative electrode slurry and preparation method thereof |
| CN108807955A (en) * | 2018-08-29 | 2018-11-13 | 西安交通大学苏州研究院 | A kind of SiNPs@CA@GO composite material and preparation methods and application |
| CN109638250A (en) * | 2018-12-11 | 2019-04-16 | 佛山市实达科技有限公司 | A kind of anode plate for lithium ionic cell of quickly-chargeable |
| CN109638250B (en) * | 2018-12-11 | 2022-04-08 | 佛山市实达科技有限公司 | Lithium ion battery negative plate capable of being rapidly charged |
| JP2022500835A (en) * | 2019-03-20 | 2022-01-04 | 寧徳新能源科技有限公司Ningde Amperex Technology Limited | Negative electrode active material, its manufacturing method, and equipment using the negative electrode active material |
| WO2020186799A1 (en) * | 2019-03-20 | 2020-09-24 | Ningde Amperex Technology Limited | Anode active material and preparation method thereof, and device using the anode active material |
| JP7354231B2 (en) | 2019-03-20 | 2023-10-02 | 寧徳新能源科技有限公司 | Negative electrode active material, method for producing the same, and device using the negative electrode active material |
| CN110323445A (en) * | 2019-06-25 | 2019-10-11 | 西安交通大学苏州研究院 | PAA-CA complex phase binder and preparation method thereof |
| CN112736247A (en) * | 2019-10-28 | 2021-04-30 | 广州汽车集团股份有限公司 | Water-based composite binder, negative electrode slurry and preparation method thereof, negative electrode sheet, lithium ion battery cell, lithium ion battery pack and application thereof |
| CN113394363B (en) * | 2020-03-13 | 2022-05-20 | 宁德新能源科技有限公司 | Preparation method of negative pole piece, battery and electronic device |
| CN113394363A (en) * | 2020-03-13 | 2021-09-14 | 宁德新能源科技有限公司 | Preparation method of negative pole piece, battery and electronic device |
| CN113889623A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Silicon negative electrode material, preparation method thereof and lithium ion battery |
| CN113889623B (en) * | 2020-07-02 | 2023-08-08 | 中国石油化工股份有限公司 | Silicon anode material, preparation method thereof and lithium ion battery |
| CN112038570A (en) * | 2020-09-22 | 2020-12-04 | 合肥国轩高科动力能源有限公司 | Silicon-carbon cathode slurry, slurry mixing method and application |
| CN113839009A (en) * | 2021-08-23 | 2021-12-24 | 惠州锂威新能源科技有限公司 | Negative electrode slurry and preparation method thereof, negative electrode plate and secondary battery |
| CN113764625A (en) * | 2021-08-26 | 2021-12-07 | 蜂巢能源科技有限公司 | Sulfide silicon-based negative plate, preparation method thereof and all-solid-state lithium ion battery |
| CN114335521A (en) * | 2021-11-22 | 2022-04-12 | 惠州市豪鹏科技有限公司 | Negative plate material, negative plate, battery preparation method and battery |
| CN117293314A (en) * | 2023-09-25 | 2023-12-26 | 浙江煌能新能源科技有限公司 | Adhesive for improving electrical property of silicon-based negative electrode, battery negative electrode and application |
| CN117293314B (en) * | 2023-09-25 | 2024-04-12 | 浙江煌能新能源科技有限公司 | Adhesive for improving electrical property of silicon-based negative electrode, battery negative electrode and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105304858B (en) | 2017-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105304858A (en) | Lithium ion battery, negative plate thereof and preparation method thereof | |
| CN103326027B (en) | A kind of negative electrode of lithium ion battery and lithium ion battery | |
| CN110690436B (en) | Negative electrode material, preparation method thereof, prepared negative electrode plate and lithium ion battery | |
| CN102637859B (en) | Lithium ion battery, graphite cathode material of lithium ion battery, and preparation method of graphite anode material | |
| CN103311515B (en) | A kind of graphene-based silicon-carbon composite cathode material and preparation method thereof | |
| CN102306759B (en) | Silicon monoxide composite cathode material for lithium ion battery, and preparation method thereof | |
| CN102569740B (en) | A kind of anode slurry of lithium iron phosphate battery makes and coating process | |
| CN105845906B (en) | Phosphorous anode material and preparation method thereof and lithium ion battery | |
| CN102185126B (en) | The process for dispersing of microscale-nanoscale electrode material | |
| Sun et al. | Effect of poly (acrylic acid)/poly (vinyl alcohol) blending binder on electrochemical performance for lithium iron phosphate cathodes | |
| CN108075125A (en) | A kind of graphene/silicon anode composite and its preparation method and application | |
| CN107546363B (en) | Negative electrode tab and lithium ion battery | |
| CN104347856A (en) | Lithium ion battery | |
| CN104795541A (en) | Lithium-ion battery negative electrode slurry preparation method | |
| CN102769149B (en) | The manufacture method of polymer Li-ion battery and polymer Li-ion battery | |
| CN1960040A (en) | High-powered lithium ferric phosphate dynamic battery, and preparation technique | |
| CN111244455A (en) | Silicon-carbon composite negative electrode material composite conductive agent of lithium ion battery, negative plate and preparation method of negative plate | |
| CN104241696A (en) | Lithium ion battery with high energy density and preparation method of lithium ion battery with high energy density | |
| CN104877593A (en) | Lithium ion battery cathode binder, cathode and battery | |
| CN114613974B (en) | Long-life quick-charging type lithium ion battery cathode material and preparation method thereof | |
| CN108682862A (en) | A kind of preparation method of lithium ion battery silicon substrate negative plate | |
| CN104795568A (en) | Lithium-ion power battery negative electrode slurry preparation method | |
| CN106129347B (en) | Porous silicon composite cathode material and preparation method thereof and lithium ion battery | |
| CN102437369B (en) | Lithium ion battery | |
| CN104766976A (en) | Lithium ion secondary battery negative pole piece and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |