CN104497190B - A kind of preparation method of the partial fluorine ethylene polymer for lithium ion battery electrode material binding agent - Google Patents

A kind of preparation method of the partial fluorine ethylene polymer for lithium ion battery electrode material binding agent Download PDF

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CN104497190B
CN104497190B CN201410833131.8A CN201410833131A CN104497190B CN 104497190 B CN104497190 B CN 104497190B CN 201410833131 A CN201410833131 A CN 201410833131A CN 104497190 B CN104497190 B CN 104497190B
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vinylidene
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ethylene polymer
lithium ion
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CN104497190A (en
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苗国祥
陈炜
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ZHEJIANG FLUORINE CHEMICAL NEW MATERIAL CO Ltd
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Abstract

The preparation method of a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, belongs to technical field of fluorine chemical industry.Comprise the following steps: 1) in polymerization reaction kettle, add deionized water, dispersant, pH adjusting agent, chain-transferring agent, vinylidene, second comonomer;2) reactor is warming up to 32 52 DEG C, reaction pressure 6.0 9.0Mpa, rotating speed 800 1600r/min, add initiator, terminate reaction after 48 hours, prepare partial fluorine ethylene polymer slurry;3) polymer paste deaerated, wash, be dried prepared finished product.The preparation method of above-mentioned a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, obtain super high molecular weight, fine grain, high-purity, the partial fluorine ethylene polymer of high high temperature resistant coloring, with the lithium ion battery of this polymer, there is the advantage that consumption of binder is few, peel strength is high, energy density is big, circulation volume conservation rate is high.

Description

A kind of preparation method of the partial fluorine ethylene polymer for lithium ion battery electrode material binding agent
Technical field
The invention belongs to technical field of fluorine chemical industry, the preparation method of a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent.
Background technology
Lithium ion battery owing to having that energy density is high, quality light and handy, stable operating voltage, have extended cycle life, a series of outstanding advantages such as security performance is high, environmental pollution is little, be widely used at present in all kinds of digital electronic goods.The electrode of lithium ion battery is formed on collector body surface by binding agent by the coated method of positive and negative electrode material.Accordingly act as the material of binding agent and must possess following principal character: 1) make active substance mutually bond and bond on the current collector;2) electrochemical stability, does not react with electrolyte and dissolves each other;3) consumption the most just has enough adhesion strengths, and film will not come off from collector body, produces slight crack;4) purity is high, and impurity is few, invariance under high temperature.At present, the most commonly used binding agent of lithium ion battery applications is Kynoar.
The preparation method of Kynoar, it is known that conventional method have polymerisation in solution, emulsion polymerization, three kinds of methods of suspension polymerisation.Polymerisation in solution is commonly used for preparing the coating polymer of lower molecular weight (Mw≤20w, η≤1.0dl/L);Emulsion polymerization is the method preparing partial fluorine ethylene polymer being most widely used in current commercial scale, it is applied to the medium (Mw≤80w of molecular weight product of lithium battery binding agent, η≤2.0dl/L), ratio shared in the compounding ingredient of general lithium battery is 3.0 5.0%, in order to obtain the lithium ion battery of higher energy density, the content of active substance have to be improved, on the premise of ensureing adhesive property, it is reduced as far as the consumption of binding agent, this partial fluorine ethylene polymer being accomplished by producing higher molecular weight by suspension method.
Due to the characteristic of suspension polymerization self, relatively big (mean diameter D50 >=80 μm) the relatively emulsion polymer of the particle diameter of polymerizate exceeds more than an order of magnitude, and in the application of lithium battery, its dissolubility receives great limitation.If polymer is not completely dissolved, the most not only can not well-bonded powdery electrode material, and when, after electrode material and adhesive coated, surface irregularity is whole, tearing strength declines, and affects battery performance.Furthermore owing to polyvinylidene fluoride homopolymer belongs to the non-interactive material of rigid structure, lacking certain flexibility, itself is the poorest to the caking property of metal, so certainly will require that the structure improving Kynoar is to adapt to actual application.
Patent CN 103755858 A discloses the solution polymerization process of a kind of polyvinylidene fluoride copolymer.The method introduces hexafluoropropene and vinylidene copolymerization by appropriate, improves the flexibility of polymer, but the molecular weight of polymer is the highest, it is impossible to be used as the binding agent of lithium ion battery.
Patent CN 103387633 A discloses the preparation method of a kind of ultra-high molecular weight poly (vinylidene fluoride) material.The method by the way of emulsion is polymerized by vinylidene, acrylic ester monomer copolymerization, need in the course of the polymerization process to add substantial amounts of surfactant, polymerization temperature is the highest, there will be the incomplete low molecular compound of reaction unavoidably, therefore the purity of product does not reaches the requirement of lithium battery binding agent, and high temperature coloring is also inevitable very poor.
Patent CN 103467631A discloses the manufacture method of a kind of vinylidene fluoride polymer with high temperature coloring resistance.The acid adding acidic materials in the polymer slurries after suspension polymerization is used to add step and the polymer slurries after polyreaction carries out the dehydration being dehydrated, the low molecular organic material eliminating auxiliary agent in polymerization process with this or the oligomer produced by the reaction of auxiliary agent with vinylidene fluoride monomers, and then improve the high temperature resistant coloring of product.But this method needs to accurately control the addition of acidic materials and temperature-rise period repeatedly, finally also needs to baking oven and is dried for a long time, is unfavorable for that scale operates.
Patent CN 103113501 A discloses a kind of method that transformation prepares Kynoar, polymerization point two sections is carried out, first it is monomer and initiator pre-polymerization in prepolymerization reactor, generate seed particles, then during product flows into prepolymer repolymerization still, adding and the monomer of prepolymer equivalent, continue polymerization, end product is size-reduced, sieving gets product.The defect of the method maximum is that the particle diameter of product is too big, is unfavorable for dissolving, and the operation of double reactor is unfavorable for the continuity of flow process, and high temperature resistant coloring and the molecular size range of product are not specifically discussed by the method.
Summary of the invention
For the above-mentioned problems in the prior art, the technical scheme of the preparation method of the partial fluorine ethylene polymer for lithium ion battery electrode material binding agent of design a kind of high-purity of offer, high molecular, high high temperature resistant coloring, low particle diameter is provided, reducing it in lithium ion battery while consumption, adhesive property can also be kept with flying colors, lithium battery goods constant current circulation volume conservation rate is higher, energy density is bigger, has development prospect widely.
The preparation method of described a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that comprise the following steps:
1) in airtight polymerization reaction kettle, nitrogen deoxygenation is purged, add deionized water, dispersant, pH adjusting agent, chain-transferring agent, vinylidene, second comonomer, the consumption of described deionized water is the 200-300% of vinylidene quality, the consumption of described dispersant is the 0.08-0.25% of vinylidene quality, the consumption of described pH adjusting agent is the 0.05-0.15% of vinylidene quality, the consumption of described chain-transferring agent is the 0.2-1.5% of vinylidene quality, and the consumption of described second comonomer is the 2.6-7.2% of vinylidene quality;
Described dispersant is one or more mixture in methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, polyvinyl alcohol;Described pH adjusting agent is one or more mixture in sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, sodium acid pyrophosphate;Described chain-transferring agent is the one in diethyl carbonate, ethyl acetate, isopropanol;Described second comonomer is one or more mixture in acrylic acid, acrylic acid methyl ester., ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate;
2) in 80 200min, temperature of reaction kettle is increased to 32 52 DEG C, reaction pressure is 6.0 9.0Mpa, rotating speed is 800 1600r/min, add initiator, reaction is terminated after 48 hours, prepare partial fluorine ethylene polymer slurry, described initiator be 10 hours half life temperature T10 be the polymerization initiator of 30~60 DEG C, the consumption of described initiator is the 0.03 0.20% of vinylidene quality;
3) polymer paste is deaerated, reclaim unreacted monomer, be washed with deionized slurry to cleaning mixture electrical conductivity and be down to 1 below μ s/cm, and then carry out being spray-dried prepared finished product by the slurry of 25-55% concentration.
The preparation method of described a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterized in that in step 1): the consumption of described deionized water is the 220-280% of vinylidene quality, the consumption of described dispersant is the 0.1-0.2% of vinylidene quality, the consumption of described pH adjusting agent is the 0.08-0.12% of vinylidene quality, the consumption of described chain-transferring agent is the 0.5-1.0% of vinylidene quality, and the consumption of described second comonomer is the 3-6% of vinylidene quality.
The preparation method of described a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterized in that in step 1): the consumption of described deionized water is the 250-260% of vinylidene quality, the consumption of described cellulose is the 0.15-0.18% of vinylidene quality, the consumption of described pH adjusting agent is the 0.1-0.11% of vinylidene quality, the consumption of described chain-transferring agent is the 0.6-0.8% of vinylidene quality, and the consumption of described second comonomer is the 4-5% of vinylidene quality.
The preparation method of described a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that in step 1): described deionized water resistivity is at more than 10M Ω.
The preparation method of described a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that step 2) in: polymerization temperature preferably 35 48 DEG C, more preferably 40 44 DEG C;Polymerization pressure preferably 6.5 8.5MPa, more preferably 7.0 8.0MPa.
The preparation method of described a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that step 2) in: rotating speed is 1000 1200r/min, preferably 1100r/min;Response time is 5-7 hour;The consumption of described initiator is the 0.05 0.15% of vinylidene quality, preferably 0.08 0.1%.
The preparation method of described a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that in step 3): be spray-dried the concentration preferably 30 50%, more preferably 35 45% of polymer paste used;Spray drying temperature preferably 80 130 DEG C, more preferably 90 120 DEG C.
The preparation method of described a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that in step 3): cleaning mixture electrical conductivity is down to 0.8 below μ s/cm.
The preparation method of above-mentioned a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, use the mode of suspension copolymerization, finally give super high molecular weight, fine grain, high-purity, the partial fluorine ethylene polymer of high high temperature resistant coloring, with the lithium ion battery of this polymer, there is the advantage that consumption of binder is few, peel strength is high, energy density is big, circulation volume conservation rate is high.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.
In following enforcement and comparative example, method of testing and condition are as follows:
Rotary viscosity is to be dissolved in N-Methyl pyrrolidone (NMP) with 1:12 by partial fluorine ethylene polymer, under the conditions of 25 DEG C, obtains with Digital Viscometer 3# rotor measurement.
Logarithmic viscosity number is addition 0.1g partial fluorine ethylene polymer in 25mL dimethyl acetylamide (DMAC) solution, after 4h dissolves completely, this solution maintains 30 DEG C and tries to achieve with the Φ 0.59 determination of ubbelohde viscometer delivery time.
Number-average molecular weight (Mn) and weight average molecular weight (Mw) are to be tested by chromatograph of gel permeation, test condition: solvent dimethylformamide (DMF), test temperature 40 DEG C.
Mean diameter (D50) is to be recorded in isophorone solution by laser particle size analyzer humid analysis.
Yellowness index is by measuring partial fluorine ethylene polymer at 140 DEG C, yellow colour index mathematic interpolation before and after 72h is aging and obtain.
High temperature resistant coloring is at 260 DEG C by visualization partial fluorine ethylene polymer, the color distortion before and after 65min baking.
Fusing point is the peak melting by differential scanning calorimeter scanning partial fluorine ethylene polymer.
Dissolution time is to be dissolved in N-Methyl pyrrolidone (NMP) with 1:20 by partial fluorine ethylene polymer, and the rotating speed with 300 stirs until time of being completely dissolved of polymer.
Performance of lithium ion battery test event: peel strength, energy density, 300 circulation after capability retention, 300 circulation after pole piece state partial fluorine ethylene polymer is joined traditional lithium-ion battery formula makes lithium ion battery after record.
Embodiment 1
In 20L autoclave, add 12Kg deionized water, 6g sodium carboxymethyl cellulose, 4.5g sodium pyrophosphate, 4.5g sodium acid pyrophosphate, 200g methyl methacrylate, purge nitrogen deoxygenation pressure testing, make oxygen content in still be less than 20ppm;Adding 2.3Kg vinylidene in initial slot, open stirring paddle, rotating speed is 1100r/min, is warming up to 47 DEG C, adds 5g perfluoroacyl peroxides with dosing pump, and 25g diethyl carbonate starts reaction;Adding vinylidene fluoride monomers with membrane pump makes reaction pressure be maintained at 7.2MPa, and after 6.2h, reaction terminates;By polymer paste in degassing tank devolatilization, reclaim unreacted monomer;It is washed with deionized polymer paste to cleaning mixture electrical conductivity and is down to 1 below μ s/cm, and then by the slurry of 35% concentration at 105 DEG C of spray drying, prepare finished product.Test performance, result is listed in table 1.
Embodiment 2
12Kg deionized water, 8g sodium carboxymethyl cellulose, 4.5g sodium pyrophosphate, 4.5g sodium acid pyrophosphate, 300g methyl methacrylate is added in 20L autoclave;Purging nitrogen deoxygenation pressure testing, makes oxygen content in still be less than 20ppm;Adding 2.4Kg vinylidene in initial slot, open stirring paddle, rotating speed is 1200r/min, is warming up to 50 DEG C, adds 4.9g perfluoroacyl peroxides with dosing pump, and 33g diethyl carbonate starts reaction;Adding vinylidene fluoride monomers with membrane pump makes reaction pressure be maintained at 7.5MPa, and after 5.6h, reaction terminates;By polymer paste in degassing tank devolatilization, reclaim unreacted monomer;It is washed with deionized polymer paste to cleaning mixture electrical conductivity and is down to 1 below μ s/cm, and then by the slurry of 36% concentration at 100 DEG C of spray drying, prepare finished product.Test performance, result is listed in table 1.
Embodiment 3
12Kg deionized water, 4.5g sodium carboxymethyl cellulose, 4.5g sodium pyrophosphate, 4.5g sodium acid pyrophosphate, 250g methyl methacrylate is added in 20L autoclave;Purging nitrogen deoxygenation pressure testing, makes oxygen content in still be less than 20ppm;Adding 2.5Kg vinylidene in initial slot, open stirring paddle, rotating speed is 1000r/min, is warming up to 48 DEG C, adds 5.6g perfluoroacyl peroxides with dosing pump, and 39g ethyl acetate starts reaction;Adding vinylidene fluoride monomers with membrane pump makes reaction pressure be maintained at 7.3MPa, and after 5.2h, reaction terminates;By polymer paste in degassing tank devolatilization, reclaim unreacted monomer;It is washed with deionized polymer paste to cleaning mixture electrical conductivity and is down to 1 below μ s/cm, and then by the slurry of 40% concentration at 108 DEG C of spray drying, prepare finished product.Test performance, result is listed in table 1.
Comparative example 1
12Kg deionized water, 1g methylcellulose is added in 20L autoclave.Purging nitrogen deoxygenation pressure testing, makes oxygen content in still be less than 20ppm;Adding 2.2Kg vinylidene in initial slot, open stirring paddle, rotating speed is 600r/min, is warming up to 77 DEG C, adds 10g di-isopropyl peroxydicarbonate with dosing pump, and 12g acetone starts reaction;Adding vinylidene fluoride monomers with membrane pump makes reaction pressure be maintained at 4.8MPa, and after 3.8h, reaction terminates.It is washed with deionized polymer paste to cleaning mixture electrical conductivity and is down to 1 below μ s/cm, and then at 85 DEG C of dry 16h, prepare finished product.Test performance, result is listed in table 1.
Comparative example 2
12Kg deionized water, 20g perfluoro caprylic acid, 12g paraffin is added in 20L autoclave.Purging nitrogen deoxygenation pressure testing, makes oxygen content in still be less than 20ppm;Adding 2.3Kg vinylidene in initial slot, open stirring paddle, rotating speed is 500r/min, is warming up to 85 DEG C, adds 10g di-isopropyl peroxydicarbonate with dosing pump, and 12g acetone starts reaction;Adding vinylidene fluoride monomers with membrane pump makes reaction pressure be maintained at 4.2MPa, and after 4.0h, reaction terminates;It is washed with deionized to cleaning mixture electrical conductivity after polymer paste is condensed and is down to 1 below μ s/cm, and then at 85 DEG C of dry 16h, prepare finished product.Test performance, result is listed in table 1.
Comparative example 3
On the basis of embodiment 1, the consumption of methyl methacrylate is 800g, and reaction temperature is 77 DEG C, and pressure is 4.8MPa, and other conditions are constant, test performance, and result is listed in table 1.
Comparative example 4
On the basis of embodiment 2, the consumption of sodium carboxymethyl cellulose is 4g, and rotating speed is 1000r/min, and other conditions are constant, test performance, and result is listed in table 1.
Table one partial fluorine ethylene polymer performance test
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Rotary viscosity/mpas 13100 12000 10700 7800 6000 9400 11700
Logarithmic viscosity number/dl/g 4.5 4.1 3.7 2.8 1.9 3.3 3.9
Mn/g/mol 698344 649359 593528 436614 379086 341320 617371
Mw/g/mol 139566 1197174 1063408 833327 775384 858426 1100347
D50/μm 33 24 42 83 8 34 56
Dissolution time/min 83 77 105 194 45 65 147
Yellowness index 0.6 0.8 0.7 2.4 36 3.4 1.0
High temperature resistant coloring White White White Light yellow Buff Light yellow White
Fusing point/DEG C 164 159 161 171 168 154 159
Peel strength/KN/m2 154 149 140 130 110 133 142
Energy density/Wh/L 480 462 435 390 374 402 443
Capability retention/% after 300 circulations 92 93 90 81 68 82 86
Pole piece state after 300 circulations Non-dry linting Non-dry linting Non-dry linting Slight dry linting Serious dry linting, dew paper tinsel Slight dry linting Non-dry linting
In performance of lithium ion battery test, embodiment, comparative example 3, comparative example 4 gained partial fluorine ethylene polymer content in lithium ion battery formula are 1.8%, and comparative example 1, comparative example 2 gained partial fluorine ethylene polymer content in lithium ion battery formula are 3%.
Result of the test shows: the partial fluorine ethylene polymer using the inventive method to prepare has high molecular weight, less particle diameter and the feature of outstanding high temperature resistant coloring;When preparing lithium ion battery with this polymer, can greatly reduce its ratio in formula and ensure solution viscosity, shortening dissolution time;With the lithium ion battery of this polymer, there is the advantage that peel strength is high, energy density is big, circulation volume conservation rate is high.
The present invention is described in detail by above technical scheme and embodiment, but is not limited to the scope of the present invention.Should be appreciated that enlightenment based on the present invention, those skilled in the art for the present invention any obvious conversion or replacement, it should also be considered as protection scope of the present invention.

Claims (8)

1. the preparation method for the partial fluorine ethylene polymer of lithium ion battery electrode material binding agent, it is characterised in that comprise the following steps:
1) in airtight polymerization reaction kettle, nitrogen deoxygenation is purged, add deionized water, dispersant, pH adjusting agent, chain-transferring agent, vinylidene, second comonomer, the consumption of described deionized water is the 200-300% of vinylidene quality, the consumption of described dispersant is the 0.08-0.25% of vinylidene quality, the consumption of described pH adjusting agent is the 0.05-0.15% of vinylidene quality, the consumption of described chain-transferring agent is the 0.2-1.5% of vinylidene quality, and the consumption of described second comonomer is the 2.6-7.2% of vinylidene quality;
Described dispersant is more than one mixture in methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, polyvinyl alcohol;Described pH adjusting agent is more than one mixture in sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, sodium acid pyrophosphate;Described chain-transferring agent is the one in diethyl carbonate, ethyl acetate, isopropanol;Described second comonomer is more than one mixture in acrylic acid, acrylic acid methyl ester., ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate;
2) in 80 200min, temperature of reaction kettle is increased to 32 52 DEG C, reaction pressure is 6.0 9.0MPa, rotating speed is 800 1600r/min, add initiator, reaction is terminated after 48 hours, prepare partial fluorine ethylene polymer slurry, described initiator be 10 hours half life temperature T10 be the polymerization initiator of 30~60 DEG C, the consumption of described initiator is the 0.03 0.20% of vinylidene quality;
3) polymer paste is deaerated, reclaim unreacted monomer, be washed with deionized slurry to cleaning mixture electrical conductivity and be down to 1 below μ s/cm, and then carry out being spray-dried prepared finished product by the slurry of 25-55% concentration.
A kind of preparation method of the partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterized in that in step 1): the consumption of described deionized water is the 220-280% of vinylidene quality, the consumption of described dispersant is the 0.1-0.2% of vinylidene quality, the consumption of described pH adjusting agent is the 0.08-0.12% of vinylidene quality, the consumption of described chain-transferring agent is the 0.5-1.0% of vinylidene quality, and the consumption of described second comonomer is the 3-6% of vinylidene quality.
A kind of preparation method of the partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterized in that in step 1): the consumption of described deionized water is the 250-260% of vinylidene quality, the consumption of described cellulose is the 0.15-0.18% of vinylidene quality, the consumption of described pH adjusting agent is the 0.1-0.11% of vinylidene quality, the consumption of described chain-transferring agent is the 0.6-0.8% of vinylidene quality, and the consumption of described second comonomer is the 4-5% of vinylidene quality.
The preparation method of a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that in step 1): described deionized water resistivity is at more than 10M Ω.
The preparation method of a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that step 2) in: polymerization temperature is 35 48 DEG C, and polymerization pressure is 6.5 8.5MPa.
The preparation method of a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that step 2) in: rotating speed is 1000 1200r/min, and the response time is 5-7 hour;The consumption of described initiator is the 0.05 0.15% of vinylidene quality.
The preparation method of a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that in step 3): be spray-dried the concentration 30 50% of polymer paste used, spray drying temperature 80 130 DEG C.
The preparation method of a kind of partial fluorine ethylene polymer for lithium ion battery electrode material binding agent, it is characterised in that in step 3): cleaning mixture electrical conductivity is down to 0.8 below μ s/cm.
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