CN103647035B - High porosity composite diaphragm and preparation method thereof, high-power battery - Google Patents

High porosity composite diaphragm and preparation method thereof, high-power battery Download PDF

Info

Publication number
CN103647035B
CN103647035B CN201310698651.8A CN201310698651A CN103647035B CN 103647035 B CN103647035 B CN 103647035B CN 201310698651 A CN201310698651 A CN 201310698651A CN 103647035 B CN103647035 B CN 103647035B
Authority
CN
China
Prior art keywords
described
composite diaphragm
high
barrier film
nano
Prior art date
Application number
CN201310698651.8A
Other languages
Chinese (zh)
Other versions
CN103647035A (en
Inventor
朱继涛
李斌
Original Assignee
深圳市慧通天下科技股份有限公司
厦门慧通天下新能源有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 深圳市慧通天下科技股份有限公司, 厦门慧通天下新能源有限公司 filed Critical 深圳市慧通天下科技股份有限公司
Priority to CN201310698651.8A priority Critical patent/CN103647035B/en
Publication of CN103647035A publication Critical patent/CN103647035A/en
Application granted granted Critical
Publication of CN103647035B publication Critical patent/CN103647035B/en

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2/00Constructional details or processes of manufacture of the non-active parts
    • H01M2/14Separators; Membranes; Diaphragms; Spacing elements
    • H01M2/16Separators; Membranes; Diaphragms; Spacing elements characterised by the material
    • H01M2/164Separators; Membranes; Diaphragms; Spacing elements characterised by the material comprising non-fibrous material
    • H01M2/166Mixtures of inorganic and organic non-fibrous material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries

Abstract

The invention provides a kind of high porosity composite diaphragm and preparation method thereof, high-power battery, the beneficial effects of the present invention is and provide a kind of high porosity composite diaphragm, the porosity that possesses of its barrier film is more than 58%, add the space storing electrolyte content in barrier film, and strengthen lithium ion in barrier film through ability.In addition barrier film also can possess 150 degree of receipts dimensional stability to heating in house high-performance less than 2%, and this barrier film has good chemical property.

Description

High porosity composite diaphragm and preparation method thereof, high-power battery

Technical field

The present invention relates to field of lithium ion battery, refer in particular to a kind of high porosity composite diaphragm and preparation side thereof Method, high-power battery.

Background technology

Lithium ion battery is the most all made up of positive pole negative material, electrolyte and barrier film, at lithium ion battery Barrier film between positive pole and negative pole is the important component part of lithium ion battery.Lithium ion battery septation is main Effect is:

(1) completely cut off positive and negative electrode and make inside battery electronics not pass freely through;

(2) ion in electrolytic liquid can be allowed to pass freely through at positive and negative interpolar.

In barrier film, the conducting power of lithium ion is directly connected to the overall performance of lithium electricity battery, high current charge-discharge Under to lithium ion ducting capacity require higher, the porosity of barrier film just directly affects the conducting power of lithium ion, Porosity is the biggest, and ionic conduction ability is the strongest, and the internal resistance of cell is the lowest, and large current density power is the best.

Under high current charge-discharge or under battery abnormal conditions, internal temperature of battery is higher, general polyolefin Barrier film is easy to appearance and causes the short circuit of inside battery both positive and negative polarity large area because shrinking excessive, and security incident occurs. It addition, lithium ion battery is under high magnification or high current charge-discharge, the barrier film that porosity is low is easily caused lithium metal Deposit in negative terminal surface, form a large amount of dendrite.These dendrite pierce through barrier film when growing to certain, cause battery Internal short-circuit thus cause potential safety hazard;Therefore, it is possible to say, High-performance diaphragm is to build safety high power One of key component of lithium ion battery.

Common lithium ion battery separator mainly has polyethylene (PE), polypropylene (PP) and PP/PE/PP tri- Layer barrier film.Membrane for polymer light weight, has good electronic isolation performance, and its deficiency is that polymer is the most molten Point is relatively low, and battery is high-multiplying power discharge or generation heat abuse when, and the heat localization of inside battery makes polymer Barrier film easily occurs thermal contraction to deform, thus causes the direct contact short circuit of both positive and negative polarity.And the porosity of conventional separator Between 35%-40%, heavy-current discharge performance is poor.

The feature of high power lithium battery is: can get substantial amounts of energy at short notice.At higher current densities, Should there is not the interruption of voltage.General by making negative pole and positive electrode active materials optimization, battery makes meanwhile Barrier film should have higher ionic conduction ability, make battery have alap internal resistance.Such as front institute Stating, common diaphragm has reached the technological limit that cannot go beyond in these parameters.

Someone uses the composite diaphragm formed at membrane surface coating aluminium sesquioxide can effectively promote battery at present Security performance, but the preparation method of this barrier film needs to use substantial amounts of organic toxic solvents, to producing into This and environmental requirement are higher.And the porosity of composite diaphragm prepared by most of this mode is the highest, to electricity The high rate during charging-discharging in pond does not help.

Summary of the invention

It is an object of the invention to overcome drawbacks described above, it is provided that a kind of simple, low cost, environmental friendliness, High porosity composite diaphragm being prone to industrialized production and preparation method thereof, high-power battery.

The object of the present invention is achieved like this: a kind of high porosity composite diaphragm, and it includes film substrate, It is respectively equipped with coating in film substrate both side surface;Described coating has loose structure, and described aperture is 20-100 Nanometer;Described coating composition is the complex of nano-inorganic substance and high molecular polymer;Described organic polymer Component of polymer includes binding agent and dispersant;

In said structure, described film substrate is polyethene microporous membrane.

In said structure, described film substrate thickness 8-12 Miao's rice, thick coating Miao's 4-8 rice.

In said structure, the mean diameter of the nano-inorganic substance of described coating is not more than 1000 nanometers.

In said structure, the nano-inorganic substance accounting example of described coating is not less than 90%.

In said structure, described organic high molecular polymer composition includes binding agent and dispersant;Described bonding Agent is the one in acrylate copolymer, acrylic styrene copolymer and BS Or it is several.

In said structure, state organic high molecular polymer composition and include binding agent and dispersant;Described dispersant Molecular weight is 5.0 × 103~30.0 × 105

The invention still further relates to a kind of high-power battery, it includes shell, encapsulates its interior battery core and electrolyte; Described battery core is by positive pole, barrier film, negative pole winding or is laminated;It thes improvement is that: described barrier film For high porosity composite diaphragm as above.

The invention still further relates to a kind of high porosity composite diaphragm preparation method, it includes step

A), dispersant is dissolved in deionized water formation aqueous solution;

B), nano-inorganic substance dispersion is formed float in aqueous;

C) in float, add binding agent and pore creating material forms coating slurry;In described coating slurry, go Ionized water accounts for 45~50wt%(mass percents), pore creating material accounts for 12~18wt%, nano-inorganic substance account for 36~ 38wt%, binding agent accounts for 1.6~3.6wt%, and dispersant accounts for 0.2~0.8wt%;

The both side surface that D), slurry is coated uniformly on film substrate forms product;

E), product is placed air-supply baking and form high porosity composite diaphragm;

In said method, described pore creating material is preferably one or both in isopropanol and N-Methyl pyrrolidone.

Step B described in said method is specifically, add nano-inorganic substance in solution and with rotating speed be 2000~3500 revs/min are stirred 1-4 hour, then carry out ultrasonic disperse 10-30 minute;Described step Rapid C is specifically, add sticker emulsion with pore creating material solvent with 600~1500 revs/min of stirrings 0.5~1.5 Hour.

Step D described in said method is specifically, pass through dipping or rollon or the side of spraying by coating slurry Formula is respectively coated on the both side surface up and down of film substrate and forms product;Described step E specifically, air blast with 38~50 degrees Celsius, 10-40 cube m/h is dried 5~10 minutes to described product.

Compared to common barrier film and preparation technology thereof, the beneficial effects of the present invention is and provide a kind of high hole Gap rate composite diaphragm, the porosity that possesses of its barrier film is more than 58%, adds and store electrolyte content in barrier film Space, and strengthen lithium ion in barrier film through ability.In addition barrier film also can possess 150 degree of receipts dimensional stability to heating in house High-performance less than 2%, and this barrier film has good chemical property.

Accompanying drawing explanation

The concrete structure of the present invention is described in detail in detail below in conjunction with the accompanying drawings

Fig. 1 is the application experiment test data of the present invention.

Detailed description of the invention

By describing the technology contents of the present invention, structural feature in detail, being realized purpose and effect, below in conjunction with Embodiment also coordinates accompanying drawing to be explained in detail.

The present invention relates to a kind of high porosity composite diaphragm, it includes film substrate, in film substrate both sides table Face is respectively equipped with coating;Described coating has loose structure, and described aperture is 20-100 nanometer;Described coating Composition is the complex of nano-inorganic substance and high molecular polymer;Described organic high molecular polymer composition includes Binding agent and dispersant.

Being different from common barrier film, this product is distributed Miao's 20-100 rice different pore size size at coat inside Loose structure, thus the porosity significantly improving composite diaphragm can be put forward, increase and composite diaphragm stores electrolyte Amount space, and strengthen lithium ion in composite diaphragm through ability.

Above-mentioned film substrate can use ultra-thin microporous polyolefin film as known in the art, in one embodiment, This patent use polyethene microporous membrane as film substrate, polyethene microporous membrane advantage at itself as base material Say thinner, and porosity is evenly.

Generally speaking, the film substrate in high porosity composite diaphragm is the thinnest, the paintable painting of its both side surface Layer can be the thickest, and thick coating, in it, the voidage chance of porous is the highest, absorbable more electrolyte. But, film substrate also can not be the thinnest, therefore, by repeatedly testing in a large number, as an embodiment, above-mentioned Middle film substrate thickness 8-12 Miao's rice, the coating of coating then corresponding optional thick Miao's 4-8 rice, i.e. two sides has added Carry out thickness and can reach Miao's 8-16 rice, thus can reach optimal counterbalance effect.

As an embodiment, in said structure, the nano-inorganic substance accounting example of described coating is not less than 90%. The coating heat resistance that thus can make complex preferably can significantly improve the resistance to of pure organic film substrate Hot property so that whole high porosity composite diaphragm has preferable heat stability, can significantly reduce battery by The potential safety hazard of thermal initiation.

As an embodiment, the mean diameter of the nano-inorganic substance of above-mentioned coating is not more than 1000 nanometers.Nanometer Inorganic matter mean diameter I makes pore size distribution more concentrate.

As an embodiment, above-mentioned nano-inorganic substance is preferred Al in the common optional scope in this area2O3、ZrO2 And TiO2In one or more.

As an embodiment, described organic high molecular polymer composition includes binding agent and dispersant.In order to Film substrate is formed preferably sprawls effect, and binding agent is preferred in the common optional scope in this area: acrylic acid One or more in ester copolymer, acrylic styrene copolymer and BS.

As an embodiment, the molecular weight of the dispersant in organic high molecular polymer composition is 5.0 × 103~ 30.0×105, the dispersant of larger molecular weight can consume the dispersant of less component on the basis of in order to be effective.

As an embodiment, above-mentioned dispersant is preferably carboxymethyl cellulose sodium in the common optional scope in this area With one or more in hydroxy acrylic acid ester homopolymer.

The invention still further relates to a kind of high-power battery, it includes shell, encapsulates its interior battery core and electrolyte; Described battery core is by positive pole, barrier film, negative pole winding or is laminated;It thes improvement is that: described barrier film For high porosity composite diaphragm as above.

The invention still further relates to a kind of high porosity composite diaphragm preparation side preparing above-mentioned high porosity composite diaphragm Method, it includes step:

A), dispersant is dissolved in deionized water formation aqueous solution;

B), nano-inorganic substance dispersion is formed float in aqueous;

C) in float, add binding agent and pore creating material forms coating slurry;

In order to ensure effect, in the coating slurry now formed, deionized water accounts for 45~50wt%(mass Percentage ratio), pore creating material accounts for 12~18wt%(mass percents), nano-inorganic substance accounts for 36~38wt%(matter Amount percentage ratio), binding agent accounts for 1.6~3.6wt%(mass percents), dispersant accounts for 0.2~0.8wt%(matter Amount percentage ratio);

The both side surface that D), slurry is coated uniformly on film substrate forms product;

E), product is placed air-supply baking and form high porosity composite diaphragm.

This technique A-C is mainly uniformly mixed by dispersant, nano-inorganic substance and bonding agent and is configured to The slurry of bonding base material.Pore creating material formation coating slurry is added again in slurry, owing to there being the existence of pore creating material, After being coated on film substrate two sides, then air-supply baking ultimately form there is answering of loose structure Close coating, it is ensured that composite diaphragm possesses higher porosity.

As an embodiment, the pore creating material in said method is preferably isopropyl in the common optional scope in this area One or both in alcohol and N-Methyl pyrrolidone.This kind of pore creating material has easily acquisition, and can meet this The demand of bright method, further, itself environmentally safe low toxicity, use and have in the present invention program There is the less effective advantage of materials.

As an embodiment, described in said method in step A, dividing of every 1000g nano inorganic oxide Powder consumption is preferably 2.5~3.5g.

As an embodiment, step B described in said method is specifically, add nano-inorganic substance in solution And be 2000~3500 revs/min with rotating speed and be stirred 1-4 hour, then carry out ultrasonic disperse 10-30 and divide Clock;Described step C is specifically, add sticker emulsion and stir with 600~1500 revs/min with pore creating material solvent Mix 0.5~1.5 hour.Use the present embodiment method add, dispersion nano-inorganic substance and sticker emulsion with Pore creating material solvent can make each several part stirring mixing in the preparation of slurry be more uniformly distributed.

As an embodiment, step D described in said method is specifically, or roll coating slurry by dipping The mode of painting formula or spraying is respectively coated on the both side surface up and down of film substrate and forms product;Described step E Specifically, air blast is with 38~50 degrees Celsius, 10-40 cube m/h is dried 5~10 points to described product Clock.This way of example is used at film substrate two sides applying coating and to blow dry, it can be ensured that dried Cheng Shihe, so that the aperture of coat inside is bigger, thus strengthens the using effect of final products.

Specific embodiment 1

A kind of high porosity composite diaphragm preparation method, takes polyethene microporous membrane as base material, and its thickness is 9 μm, porosity is 40%.By 0.3g dispersant sodium carboxymethyl cellulose, (molecular weight is about 60 × 104) point Being dispersed in 105g deionized water and stir, control rotating speed is 1500r/min, stirs 0.5h.Then by 100g Al2O3(mean diameter 380nm) substep adds in solution and high-speed stirred, and control rotating speed is 2500r/min, Stirring 2h.Then ultrasonic disperse, controls ultrasonic power 100kw, controls ultrasonic time 10~30min.Again Binding agent BS emulsion 5g is added in suspension, controls speed of agitator 1500r/min, Stirring 1h, is eventually adding 45g pore creating material isopropanol, and stirring at low speed 0.5h, and control rotating speed is 1000r/min. I.e. obtain slurry.Again by slurry even application on the upper and lower surface of basic unit, control the wet-film thickness of every one side It is 10~20 μm.Then wet coating is placed in forced air drying at 38~50 DEG C, controls air quantity 30m3/ h, Control drying time 5~10min.Prepare high porosity composite diaphragm and be denoted as m1.

Specific embodiment 2

A kind of high porosity composite diaphragm preparation method, takes polyethene microporous membrane as base material, and its thickness is 9 μm, porosity is 40%.By 0.3g dispersant hydroxy acrylic acid ester homopolymer, (molecular weight is about 30 × 104) Being dispersed in 105g deionized water and stir, control rotating speed is 1500r/min, stirs 0.5h.Then by 100 The Al of g2O3(mean diameter 380nm) substep adds in solution and high-speed stirred, and controlling rotating speed is 2500 R/min, stirs 2h.Then ultrasonic disperse, controls ultrasonic power 100kw, controls ultrasonic time 10~30min. Again binding agent BS emulsion 5g is added in suspension, control speed of agitator 1500 R/min, stirs 1h, is eventually adding 45g pore creating material isopropanol, and stirring at low speed 0.5h, controls rotating speed and is 1000r/min.I.e. obtain slurry.Again by slurry even application on the upper and lower surface of basic unit, control every one side Wet-film thickness be 10~20 μm.Then wet coating is placed in forced air drying at 38~50 DEG C, controls air quantity 30m3/ h, controls drying time 5~10min.Prepare high porosity composite diaphragm and be denoted as m2.

Specific embodiment 3

A kind of high porosity composite diaphragm preparation method, takes polyethene microporous membrane as base material, and its thickness is 9 μm, porosity is 40%.By 0.3g dispersant sodium carboxymethyl cellulose, (molecular weight is about 60 × 104) point Being dispersed in 105g deionized water and stir, control rotating speed is 1500r/min, stirs 0.5h.Then by 100g Al2O3(mean diameter 380nm) substep adds in solution and high-speed stirred, and control rotating speed is 2500r/min, Stirring 2h.Then ultrasonic disperse, controls ultrasonic power 100kw, controls ultrasonic time 10~30min.Again Binding agent BS emulsion 5g is added in suspension, controls speed of agitator 1500r/min, Stirring 1h, is eventually adding pore creating material 15g N-Methyl pyrrolidone and 30g isopropanol, and stirring at low speed 0.5 H, control rotating speed is 1000r/min.I.e. obtain slurry.Again by slurry even application on the upper and lower surface of basic unit, The wet-film thickness controlling every one side is 10~20 μm.Then wet coating is placed in air blast at 38~50 DEG C do Dry, control air quantity 30m3/ h, controls drying time 5~10min.Prepare high porosity composite diaphragm to be denoted as m3。

Specific embodiment 4

A kind of high porosity composite diaphragm preparation method, takes polyethene microporous membrane as base material, and its thickness is 9 μm, porosity is 40%.By 0.3g dispersant hydroxy acrylic acid ester homopolymer, (molecular weight is about 30 × 104) Being dispersed in 105g deionized water and stir, control rotating speed is 1500r/min, stirs 0.5h.Then by 100 The Al of g2O3(mean diameter 380nm) substep adds in solution and high-speed stirred, controls rotating speed and is 2500r/min, stirs 2h.Then ultrasonic disperse, control ultrasonic power 100kw, control ultrasonic time 10~ 30min.Again binding agent BS emulsion 5g is added in suspension, control speed of agitator 1500r/min, stirs 1h, is eventually adding pore creating material 15g N-Methyl pyrrolidone and 30g isopropanol, and Stirring at low speed 0.5h, control rotating speed is 1000r/min.I.e. obtain slurry.Again by slurry even application in basic unit Upper and lower surface on, the wet-film thickness controlling every one side is 10~20 μm.Then wet coating is placed in 38~ Forced air drying at 50 DEG C, controls air quantity 30m3/ h, controls drying time 5~10min.Prepare high porosity Composite diaphragm is denoted as m4.

Specific embodiment 5

A kind of high porosity composite diaphragm preparation method, takes polyethene microporous membrane as base material, and its thickness is 9 μm, porosity is 40%.By 0.3g dispersant hydroxy acrylic acid ester homopolymer, (molecular weight is about 30 × 104) Being dispersed in 105g deionized water and stir, control rotating speed is 1500r/min, stirs 0.5h.Then by 100 The TiO of g2(mean diameter 380nm) substep adds in solution and high-speed stirred, and control rotating speed is 2500r/min, Stirring 2h.Then ultrasonic disperse, controls ultrasonic power 100kw, controls ultrasonic time 10~30min.Again Binding agent BS emulsion 5g is added in suspension, controls speed of agitator 1500r/min, Stirring 1h, is eventually adding pore creating material 15g N-Methyl pyrrolidone and 30g isopropanol, and stirring at low speed 0.5 H, control rotating speed is 1000r/min.I.e. obtain slurry.By slurry even application on the upper and lower surface of basic unit, The wet-film thickness controlling every one side is 10~20 μm.Then wet coating is placed in air blast at 38~50 DEG C do Dry, control air quantity 30m3/h, control drying time 5~10min.Prepare high porosity composite diaphragm to be denoted as m5。

Comparative example

Taking polyethene microporous membrane as base material, its thickness is 9 μm, and porosity is 40%.0.3g is disperseed (molecular weight is about 60 × 10 to agent carboxymethyl sodium cellulosate4) be dispersed in 105g deionized water and stir, control Rotating speed processed is 1500r/min, stirs 0.5h.Then ultrasonic disperse, controls ultrasonic power 100kw, controls Ultrasonic time 10~30min.Again binding agent BS emulsion 5g is added in suspension, Control speed of agitator 1500r/min, stir 1h, be eventually adding pore creating material 15g N-Methyl pyrrolidone and 30 The isopropanol of g, and stirring at low speed 0.5h, control rotating speed is 1000r/min.I.e. obtain slurry.Slurry is equal On the even upper and lower surface being sprayed on basic unit, the wet-film thickness controlling every one side is 10~20 μm.Then by wet Painting is placed on forced air drying at 38~50 DEG C, controls air quantity 30m3/h, controls drying time 5~10min. Prepare high porosity composite diaphragm and be denoted as Am1.

Membrane properties is tested, and result is shown in Fig. 1.Test condition is described as follows:

Air permeability is tested: uses air permeability instrument (4110N type Gurley Permeability gauge) to measure composite diaphragm and passes through Time required for 100mL air,

Porosity is tested: use mercury injection apparatus to measure the porosity of composite diaphragm.

Diaphragm retracts rate is tested: composite diaphragm m1-m5, Am1 and polyethylene base material film are cut into 200 × 100mm(laterally × longitudinally) strip small pieces, be then placed in the baking oven of 150 DEG C toasting 30min After, take out and measure horizontal and vertical length, and shrinkage from mold dimensions.

A kind of high power lithium ion cell, 18650 batteries with rated capacity as 1.4Ah are test model, electricity Pond internal positive material, negative material and electrolyte are identical with conventional high power battery, only by positive pole material Expect the membrane replacement between negative material be composite diaphragm obtained by the present invention (m1, m2, m3, m4, M5 and Am1).

Battery performance test, is shown in Fig. 1.Test condition is as follows:

Inner walkway: use AC internal Resistance tester (BK-300) to measure internal resistance.

Multiplying power discharging property: first, charges to 3.65V, 3.65V constant-voltage charge by battery with 0.5C, cuts Only electric current is 0.02C, shelves 5min, then by battery respectively with the current discharge of 1C, 3C, 5C and 7C To 2.5V.Multiplying power discharging conservation rate=[(capacity of 3C/5C/7C electric discharge)/1C discharge capacity] × 100%.10C Electric discharge conservation rate is shown in Fig. 1.

It can be seen from figure 1 that embodiment 4-5 is owing to using double-component pore creating material, the coating of formation has greater number Pore structure, make composite coating have a higher porosity, corresponding battery has more preferable multiplying power discharging Energy.Embodiment 5 is due to TiO2The granule of material is uniform-spherical structure, it is possible to coating central hole structure is more Closely, porosity is caused slightly to reduce than embodiment 4.TiO2And Al2O3It is all exotic material, therefore at base The coating formed on material also has resistance to elevated temperatures, by TiO2The heat resistance of composite coating the most relatively Al2O3 Composite coating slightly weakens, therefore, and the thermal contraction performance than embodiment 1-4 of the composite diaphragm in embodiment 5 Weaker.In comparative example because of coating be solution after, after dispersant in solution and binding agent can adhere to dry Stick to the surface of base material, owing to there is no the skeletal support effect of inorganic solid particles, form aperture, even The coating of the uneven distribution of atresia, causes its porosity, and heat resistance is the most worst.

The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every profit The equivalent structure made by description of the invention and accompanying drawing content or equivalence flow process conversion, or directly or indirectly transport It is used in other relevant technical fields, is the most in like manner included in the scope of patent protection of the present invention.

Claims (3)

1. a high porosity composite diaphragm preparation method, it is characterised in that: it includes step
A), dispersant is dissolved in deionized water formation aqueous solution;
B), nano-inorganic substance dispersion is formed float in aqueous;
C) in float, add binding agent and pore creating material forms coating slurry;In described coating slurry, go Ionized water accounts for 45~50wt% (mass percents), and pore creating material accounts for 12~18wt%, nano-inorganic substance account for 36~ 38wt%, binding agent accounts for 1.6~3.6wt%, and dispersant accounts for 0.2~0.8wt%;
The both side surface that D), slurry is coated uniformly on film substrate forms product;
E), product is placed air-supply baking and form high porosity composite diaphragm;
Described pore creating material is one or both in isopropanol and N-Methyl pyrrolidone;
Described step B specifically, nano-inorganic substance is added in solution and with rotating speed be 2000~3500 turns/ Minute it is stirred 1-4 hour, then carries out ultrasonic disperse 10-30 minute;Described step C specifically, Add binding agent to stir 0.5~1.5 hour with 600~1500 revs/min with pore creating material;
Described step D is specifically, be respectively coated on the upper of film substrate by coating slurry by the way of spraying Lower both side surface forms product, and the wet-film thickness controlling every one side is 10~20 μm;Described step E is concrete For, air blast is with 38~50 degrees Celsius, and 10-40 cube m/h is dried 5~10 minutes to described product;
Described film substrate is polyethene microporous membrane, and thickness is Miao's 8-12 rice, and porosity is 40%;
Described dispersant is one or more in sodium carboxymethyl cellulose and hydroxy acrylic acid ester homopolymer, point Powder molecular weight is 5.0 × 103~30.0 × 105, the dispersant dosage of every 1000g nano inorganic oxide is 2.5~3.5g;
Described binding agent is that acrylate copolymer, acrylic styrene copolymer and butadiene-styrene are total to One or more in polymers;
Described nano-inorganic substance is Al2O3、TiO2、CaCO3In one or more, mean diameter be not more than 1000 nanometers, proportion is not less than 90% in the coating.
2. the high hole that a high porosity composite diaphragm preparation method according to claim 1 prepares Gap rate composite diaphragm.
3. a high-power battery, it includes shell, encapsulates its interior battery core and electrolyte;Described battery core by Positive pole, barrier film, negative pole wind or are laminated;It is characterized in that: described barrier film is for such as claim 2 Described high porosity composite diaphragm.
CN201310698651.8A 2013-12-18 2013-12-18 High porosity composite diaphragm and preparation method thereof, high-power battery CN103647035B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310698651.8A CN103647035B (en) 2013-12-18 2013-12-18 High porosity composite diaphragm and preparation method thereof, high-power battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310698651.8A CN103647035B (en) 2013-12-18 2013-12-18 High porosity composite diaphragm and preparation method thereof, high-power battery

Publications (2)

Publication Number Publication Date
CN103647035A CN103647035A (en) 2014-03-19
CN103647035B true CN103647035B (en) 2016-08-17

Family

ID=50252226

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310698651.8A CN103647035B (en) 2013-12-18 2013-12-18 High porosity composite diaphragm and preparation method thereof, high-power battery

Country Status (1)

Country Link
CN (1) CN103647035B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104979516B (en) * 2014-04-10 2018-08-03 宁德时代新能源科技股份有限公司 The preparation method of electrochemical appliance and electrochemical appliance isolation film
CN104979512B (en) * 2014-04-10 2017-12-26 宁德时代新能源科技股份有限公司 The preparation method of electrochemical appliance, used barrier film and barrier film
CN106469798A (en) * 2015-08-19 2017-03-01 中信国安盟固利动力科技有限公司 A kind of quickly-chargeable and the excellent lithium ion battery of security performance and preparation method thereof
CN106684290B (en) * 2016-12-29 2019-10-15 宁波中科达新材料有限公司 Lithium ion battery separator and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1388993A (en) * 2000-08-12 2003-01-01 Lg化学株式会社 Multi-component composite film method for preparing the same
CN101088183A (en) * 2004-12-22 2007-12-12 Lg化学株式会社 Organic/inorganic composite microporous membrane and electrochemical device prepared thereby

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5882721A (en) * 1997-05-01 1999-03-16 Imra America Inc Process of manufacturing porous separator for electrochemical power supply

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1388993A (en) * 2000-08-12 2003-01-01 Lg化学株式会社 Multi-component composite film method for preparing the same
CN101088183A (en) * 2004-12-22 2007-12-12 Lg化学株式会社 Organic/inorganic composite microporous membrane and electrochemical device prepared thereby
CN102646802A (en) * 2004-12-22 2012-08-22 Lg化学株式会社 Organic/inorganic composite microporous separator and manufacturing method thereof, and electrochemical device

Also Published As

Publication number Publication date
CN103647035A (en) 2014-03-19

Similar Documents

Publication Publication Date Title
CN104124427B (en) Electrode, electrochemical device comprising electrode, and manufacture method of electrode
CN101471432B (en) Diaphragm and preparation method thereof as well as lithium ion battery
Liu et al. Electrochemical performance of LiFePO4 cathode material coated with ZrO2 nanolayer
Xiang et al. Enhanced high rate properties of ordered porous Cu2O film as anode for lithium ion batteries
CN102064300A (en) Porous composite diaphragm for lithium ion secondary battery and preparation method thereof
Dokko et al. High rate discharge capability of single particle electrode of LiCoO2
Jeong et al. Evaporation-induced, close-packed silica nanoparticle-embedded nonwoven composite separator membranes for high-voltage/high-rate lithium-ion batteries: Advantageous effect of highly percolated, electrolyte-philic microporous architecture
KR101198806B1 (en) Electrode of secondary cell including por0us insulating layer and manufacturing thereof
CN101891930B (en) Carbon nano tube-containing sulfur-based composite cathode material and preparation method thereof
Sakuda et al. All-solid-state lithium secondary batteries with oxide-coated LiCoO2 electrode and Li2S–P2S5 electrolyte
CN103579564B (en) A kind of ceramic diaphragm and its preparation method and application
CN103515564B (en) A kind of composite diaphragm and preparation method thereof
CN102522516A (en) Asymmetric composite diaphragm for lithium ion secondary cell and preparation method thereof
CN103078077B (en) Lithium ion battery diaphragm with special structure and preparation method thereof
CN101969110A (en) Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method
CN102969489B (en) A kind of Si-C composite material and preparation method thereof, lithium ion battery containing this material
CN103579590B (en) A kind of preparation method of clad anode material of lithium battery
CN103107301B (en) Novel lithium ion battery diaphragm with inorganic coating and preparation method thereof
CN104795249B (en) A kind of novel battery capacitance based on compound positive and negative electrode material
CN101262077A (en) A high-capacity secure 26650 lithium ion battery and its making method
CN102127828B (en) Porous nano carbon fiber material, lithium battery cathode material and cathode plate
CN103956458B (en) A kind of composite lithium ion battery anode and preparation method thereof and the application in all-solid-state battery
CN104085877A (en) Porous carbon electrode material based on chitosan and derivative of chitosan thereof as well as preparation method and application of porous carbon electrode material
CN102005611A (en) Polymer electrolyte and preparation method and application thereof
CN103102717B (en) Water-based ceramic coating for lithium ion battery and application thereof

Legal Events

Date Code Title Description
PB01 Publication
TA01 Transfer of patent application right

Effective date of registration: 20140320

Address after: 518000 Liantang District, Guangming Village, Gongming street, Shenzhen, Guangdong Province, C

Applicant after: Shenzhen Wisewod Technology Co., Ltd.

Applicant after: Xiamen Huitong Tianxia New Energy Co., Ltd.

Address before: 518000 Liantang District, Guangming Village, Gongming street, Shenzhen, Guangdong Province, C

Applicant before: Shenzhen Wisewod Technology Co., Ltd.

ASS Succession or assignment of patent right

Owner name: XIAMEN HUITONG TIANXIA NEW ENERGY CO., LTD.

Effective date: 20140320

C41 Transfer of patent application or patent right or utility model
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
COR Change of bibliographic data
CB03 Change of inventor or designer information

Inventor after: Zhu Jitao

Inventor after: Li Bin

Inventor before: Li Bin

Inventor before: Zhu Jitao

C14 Grant of patent or utility model
GR01 Patent grant
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Zhu Jitao

Inventor after: Li Bin

Inventor after: Wang Hailong

Inventor before: Zhu Jitao

Inventor before: Li Bin

PP01 Preservation of patent right

Effective date of registration: 20190715

Granted publication date: 20160817

PP01 Preservation of patent right